RXNO is the name reaction ontology. It contains more than 500 classes representing organic reactions such as the Diels–Alder cyclization.
imported from
This relation obtains between a planned process and a objective specification when the criteria specified in the objective specification are met at the end of the planned process.
The notion here is that a given reaction is meant to 'protect' a given group from reacting in a subsequent process and can be 'deprotected' later.
can we chain 'has specified reactant' (RXNO:0000424) and has_part ?
If a reaction R deprotects a group G, then G is in the product where it wasn't in the reactant.
can we chain 'has specified product' (RXNO:0000423) and has_part ?
A relation between a planned reaction step and a molecular entity participating in that process. The creation of the molecular entity during the process is explicitly specified in the objective specification which the planned reaction step realizes the concretization of.
The difference between this and OBI's has_specified_output is that it is necessary that the participant starts to exist during the process.
A relation between a planned reaction step and a molecular entity participating in that process that is not created during the process. The destruction of the molecular entity during the process is explicitly specified in the plan specification which the process realizes the concretization of.
The difference between this and OBI's has_specified_input is that it is necessary that the reactant ceases to exist during the process.
A relation between a planned reaction step and a molecular entity participating in that process that has_role catalyst ((CHEBI:35223).
A relation between a planned reaction step and a molecular entity participating in that process. The creation and subsequent destruction of the molecular entity during the process are explicitly specified in the plan specification which the process realizes the concretization of.
An alpha-oxyketone that has a hydroxy group as the alpha-oxy moiety.
An organic hydroxy compound that consists of benzene bearing a single hydroxy substituent. The parent of the class of phenols.
An azane that consists of a single nitrogen atom covelently bonded to three hydrogen atoms.
Compounds having the structure RSR (R =/= H). Such compounds were once called thioethers.
A one-carbon compound in which the carbon is joined only to a single oxygen. It is a colourless, odourless, tasteless, toxic gas.
An organosilicon compound that is benzene in which a hydrogen is replaced by a silyl group.
A compound containing at least one carbon-halogen bond (where X is a halogen atom).
An elemental molecule consisting of two trivalently-bonded nitrogen atoms.
A manganese group element atom that has formula Mn.
An acyclic branched or unbranched hydrocarbon having the general formula CnH2n+2, and therefore consisting entirely of hydrogen atoms and saturated carbon atoms.
Acyclic branched or unbranched hydrocarbons having a carbon-carbon triple bond and the general formula CnH2n-2, RC#CR.
Any benzenoid aromatic compound consisting of the benzene skeleton and its substituted derivatives.
Salts and C-organyl derivatives of hydrogen cyanide, HC#N.
A compound derived from a hydrocarbon by replacing a hydrogen atom with a halogen atom.
Any member of the class of toluenes bearing one or more nitro substituents on the benzene ring.
A compound having bonds between one or more metal atoms and one or more carbon atoms of an organyl group.
An organosilicon compound is a compound containing at least one carbon-silicon bond.
Derivatives of oxoacids RnE(=O)OH in which the hydroxy group is replaced by an amino group and the oxo group is replaced by =NR. In organic chemistry an unspecified amidine is commonly a carboxamidine.
A molecular entity possessing an unpaired electron.
Any member of the class of benzenes that is a substituted benzene in which the substituents include one (and only one) methyl group.
An organosulfur compound in which a thiol group, -SH, is attached to a carbon atom of any aliphatic or aromatic moiety.
An indolinone carrying an oxo group at position 2.
A molecular entity all atoms of which have the same atomic number.
A cyclic compound having as ring members atoms of the same element only.
A homocyclic compound in which all of the ring members are carbon atoms.
A cyclically conjugated molecular entity with a stability (due to delocalization) significantly greater than that of a hypothetical localized structure (e.g. Kekule structure) is said to possess aromatic character.
A polycyclic compound in which at least one of the rings contains at least one non-carbon atom.
The isomer HN(+)#C(-) of hydrocyanic acid, HC#N, and its hydrocarbyl derivatives RNC (RN(+)#C(-)).
A compound formally derived from an oxoacid RkE(=O)l(OH)m (l > 0) and an alcohol, phenol, heteroarenol, or enol by linking with formal loss of water from an acidic hydroxy group of the former and a hydroxy group of the latter.
Any heteroatomic molecular entity that is a chemical compound of halogen with other chemical elements.
A phosphonic acid derivative in which one or both OH groups have been esterified.
Any of a class of cyclic chemical compounds that contain an unsaturated six-membered ring with one ring oxygen atom and an oxo substituent.
Any organonitrogen compound containing a cyclic component with nitrogen and at least one other element as ring member atoms.
I think this is the same as a thiacycle but need to check.
A monocyclic arene that is benzene substituted with one or more alkyl groups.
A haloalkane that is methane in which one (or more) of the hydrogens have been replaced by a halogen atom/halogen atoms.
Radicals derived from hydroxylamines by removal of the hydrogen atom from the hydroxy group. The synonymous terms nitroxyl radicals and nitroxides erroneously suggest the presence of a nitro group.
A dithiol that is propane substituted by thiol groups at positions 1 ans 3.
Ethers ROR' where R has a double bond adjacent to the oxygen of the ether linkage.
Enol ethers ROR' where R' has the structure SiR''R'''R''''.
Ethers ROR' where R' has the structure SiR''R'''R''''.
An azole in which the five-membered heterocyclic aromatic skeleton contains a N atom and one S atom.
A compound formally derived from ammonia by replacing one, two or three hydrogen atoms by organyl groups.
A compound derived from an arene by replacing a hydrogen atom with a halogen atom.
A compound containing at least one carbon-lithium bond.
A compound containing at least one carbon-magnesium bond.
A compound of general formula RC(=O)SR'. Compare with thionoester, RC(=S)OR'.
An organolithium compound where an alkyl group is bound to a lithium atom.
An alkyllithium compound that has formula C4H9Li.
A compound containing at least one carbon-zinc bond.
Any compound containing two aryl groups connected by a single C atom.
A haloketone in which the halogen and oxo substituents are on adjacent carbon atoms.
A ketone of formula RC(=O)CH3 (R =/= H).
A compound with the general formula R2C=O (R=/=H) where one or more of the R groups contains an oxy (-O-) group.
A compound having the general formula RR'C(OH)OR'' (R'' =/= H).
An organooxygen compound having the structure RR'C(OR'')(OR''') (R'', R''' =/= H). Mixed acetals have R'' and R''' groups which differ.
A chemical substance is a portion of matter of constant composition, composed of molecular entities of the same type or of different types.
A mixture is a chemical substance composed of multiple molecules, at least two of which are of a different kind.
A polymer is a mixture, which is composed of macromolecules of different kinds and which may be differentiated by composition, length, degree of branching etc..
An organic phosphonate containing a C-PO(OH)2 or C-PO(OR)2 group (where R = alkyl group).
An organic phosphonate of formula (RO)2P(=O)-CR2-NR2; R can be H.
Any monocyclic heteroarene consisting of a five-membered ring containing nitrogen. Azoles can also contain one or more other non-carbon atoms, such as nitrogen, sulfur or oxygen.
Formation of a covalent bond between a substrate and a formyl group.
Formation of a covalent bond between a substrate and an silyl group.
Formation of a covalent bond between a substrate and an alkyl group.
Formation of a covalent bond between a substrate and a hydrocarbyl group.
Formation of a covalent bond between a substrate and an aryl group.
Formation of a covalent bond between a substrate and an allyl group.
Formation of a covalent bond between a substrate and an organyl group.
Formation of a covalent bond between a substrate and an acyl group.
Formation of a covalent bond between a substrate and a sulfonyl group.
has_participant: CHEBI:51100; has_participant: CHEBI:29825
A process in which at least one of the participants is a molecule.
TODO: needs work, formal definition, etc.
Formation of a covalent bond between a substrate and a halo group.
Formation of a covalent bond between a substrate and an imino group.
Formation of a covalent bond between a substrate and a nitro group.
Formation of a ring in a molecule from a chain by formation of a new bond.
A molecular process where two or more unsaturated molecules or parts of the same molecule combine to form a cyclic adduct in which there is a net reduction of bond multiplicity.
A cycloaddition in which each participant contributes two electrons to the transformation of reactants to products.
A molecular process in which a cyclic system decomposes into two or more unsaturated molecules or parts of the same molecule and there is a net increase in bond multiplicity.
A cycloaddition in which one participant contributes four electrons and the other participant contributes two electrons to the transformation of reactants to products.
Formation of a covalent bond between a substrate and a group.
Breaking of a covalent bond between a substrate and a group.
The complete, net removal of one or mole electrons from a molecular entity, corresponding to an increase in the oxidation number of any atom within any substrate.
The complete transfer of one or more electrons to a molecular entity.
The transfer of an electron to a molecular entity, resulting in a molecular entity of increased negative charge.
A reduction in which an aldehyde is reduced to form a primary alcohol.
An oxidation process where an alcohol is transformed into a carbonyl compound.
An oxidation process where a primary alcohol is transformed into an aldehyde.
An oxidation process where a secondary alcohol is transformed into a ketone.
An oxidation process where an amine is transformed into an imine.
A reduction process where an imine is transformed into an amine.
A reduction process where the oxidation state carbonyl carbon in the ester functionality is reduced.
An ester reduction where the product is the corresponding aldehyde.
An ester reduction where the product is the corresponding primary alcohol.
A reduction process where a ketone is reduced to a secondary alcohol.
An oxidation process where the oxidation state of at least one doubly-bonded carbon atom increases.
An alkene oxidation where the product is the corresponding 1,2-diol.
An alkene oxidation where the reagent is ozone and the product is the corresponding ozonide.
An alkene oxidation process where the reactant is a primary alkene and the products are carboxylic acid and carbon dioxide. This can be achieved with a warm, acidic solution of potassium permanganate.
primary alkene oxidation to carboxylic acid and carbon dioxide
An alkene oxidation where the reactant is a tertiary alkene and the products are the corresponding carboxylic acid and ketone. This can be achieved with a warm, acidic solution of potassium permanganate.
tertiary alkene oxidation to carboxylic acid and ketone
An alkene oxidation process where the reactant is a secondary alkene and the products are the corresponding aldehydes. This can be achieved with warm, acidic potassium permanganate.
secondary, non-terminal alkene oxidation to aldehydes
An alkene oxidation process where the reactant is a secondary terminal alkene and the products are carbon dioxide and the corresponding ketone. This can be achieved by warm, acidic potassium permanganate solution.
secondary terminal alkene oxidation to ketone and carbon dioxide
An alkene oxidation process where the reactant is a quaternary alkene and the products are the corresponding ketones.
A reduction process that involves addition of hydrogen atoms across a double bond.
Formation of a covalent bond between a substrate and a pseudohalo group.
A molecular process where a molecule is broken up by reaction with a molecule that is part of the solvent material. It may be the primary constituent molecule of the solvent material (for example water, ethanol, ammonia) or its lyonium ion or lyate ion.
A solvolysis reaction where the solvent material is water.
A reaction in which two or more reactants or remote reactive sites within the same molecular entity yield a single main product with accompanying formation of a small molecule.
A condensation reaction where the small molecule produced is water.
A reaction of two or more reacting molecular entities resulting in a single reaction product containing all atoms of all components with formation of two chemical bonds and a net reduction in bond multiplicity.
Formation of a covalent bond between a substrate and an amino group.
A molecular process where two groups are lost with concomitant formation of an unsaturation in the molecule or formation of a new ring.
A cyclisation that results in the formation of an epoxide.
An oxidation process where the oxidation state of at least one sulfur atom increases.
An oxidation process where the oxidation state of at least one nitrogen atom increases.
A formal account of the degree of oxidation of an atom.
It turns out to be formally defined, which makes our definitions a bit poor.
Formation of a covalent bond between a molecule and a carboxy group.
Oxidation of a carbonyl group to an alkyne.
A cycloaddition in which one participant contributes three electrons and the other participant contributes two electrons to the transformation of reactants to products.
Molecular process in which an aldehyde or ketone tautomerises to form an enol.
Disposition that is realised in the process of enolisation
A carbonyl compound that bears the disposition to be enolised.
this surely belongs in ChEBI but put it here pro tem
Breaking of a covalent bond between an alkyl group and an oxygen atom.
A cycloaddition in which two participants contribute two electrons and the other participant contributes one electron to the transformation of reactants to products.
This term was obsoleted from the RXNO namespace and transferred to MOP because it is a process identifiable by its mechanism rather than the intention of the experimenter.
A reaction in which two or more reactants or remote reactive sites within the same molecular entity yield a single main product with accompanying formation of a carbon dioxide molecule.
A reaction in which two or more reactants or remote reactive sites within the same molecular entity yield a single main product with accompanying formation of an ethanol molecule.
accepting an electron pair in Lewis adduct formation
electron pair donation in Lewis adduct formation
Catalysis of a reaction where the catalyst either donates a hydron or accepts an electron pair.
A reaction in which one singly-bonded group, but not the hydrogen atom, is replaced by another singly-bonded group.
The Gold Book says hydrogen atoms count, but this differs from everyone's intuition. See http://goldbook.iupac.org/S06078.html
A substitution reaction in which one singly-bonded substituent on an aromatic skeleton is replaced by another singly-bonded substituent.
A substitution reaction in an allylic system with concomitant migration of the allyl double bond.
A substitution reaction where the reactive centre is a nitrogen atom.
A substitution reaction where the reactive centre is an oxygen atom.
A substitution reaction where the reactive centre is a sulfur atom.
Formation of a covalent bond with a group where the free valence is on a nitrogen centre.
formation of covalent bond with nitrogen centre
A reaction in which two or more reactants or remote reactive sites within the same molecular entity yield a single main product with accompanying formation of an alcohol molecule.
A disposition which is realised in a [4+2] reaction with a double-bonded system.
Breaking of a covalent bond between an alkyl group and a substrate.
Breaking of a covalent bond between a substrate and an organyl group.
Breaking of a covalent bond between a substrate and a halo group.
Breaking of a covalent bond between a molecule and a carboxy group.
Formation of a covalent bond between a nitrogen atom in a substrate and a methyl group.
Formation of a covalent bond between a nitrogen atom in a substrate and an alkyl group.
Formation of a covalent bond between a nitrogen atom in a substrate and an aryl group.
Formation of a covalent bond between a nitrogen atom in a substrate and an acyl group.
Formation of a covalent bond between a nitrogen atom in a substrate and a sulfonyl group.
Formation of a covalent bond between an oxygen atom in a substrate and a silyl group.
Formation of a covalent bond between an oxygen atom in a substrate and an acyl group.
Formation of a covalent bond between an oxygen atom in a substrate and a sulfonyl group.
The formation of a covalent bond between a phosphorus atom and an alkyl group.
A reaction where the number of atoms in the molecular skeleton increases.
A molecular process with which the experimenters aim to achieve a particular molecular transformation.
A reaction where a bond is formed between two carbon atoms.
An aldol condensation where an aryl aldehyde reacts with an acid anhydride to form a cinnamic acid.
A reaction in which the number of atoms in any ring changes between the reactant and the products.
This term was obsoleted because it was a grouping term that wasn't much help.
A planned reaction step where the product contains a ring that was not in any of the reactants.
A [4+2] cycloaddition reaction where a diene reacts with a compound containing a double or triple bond (a dienophile) to form an unsaturated six-membered ring compound.
A joining reaction where an alkene with an allylic hydrogen reacts with a compound containing a multiple bond (an enophile) to form a substituted alkene.
A joining reaction where a nucleophile adds to the beta-carbon of an alpha,beta-unsaturated system (or an activated carbon-carbon bond).
A conjugate addition reaction where a carbon nucleophile adds to the beta-carbon of an alpha,beta-unsaturated system (or an activated carbon-carbon bond).
A reaction where the number of atoms in the skeleton, and their connectivity, remain the same.
A reaction in which a functional group undergoes a change that does not affect the number of atoms in (or connectivity of) the skeleton of the molecule.
A functional group modification reaction where a functional group is oxidised.
A functional group oxidation where an aromatic amine is transformed into an aromatic diazonium salt.
A carbon-carbon coupling reaction where a Grignard reagent reacts with a compound containing an electrophilic carbon atom. A Grignard reagent is a magnesium-stabilised carbon nucleophile. An aldehyde leads to a secondary alcohol, a ketone leads to a tertiary alcohol, an ester leads to a ketone and a nitrile leads to a ketone.
A carbon-carbon coupling reaction where a carbonyl compound reacts with a phosphonium ylide to give an alkene.
A carbon-carbon coupling reaction where an enol or enolate reacts with a carbonyl compound to form a beta-hydroxy ketone. The name comes from aldehyde + alcohol.
An aldol addition where an enol or enolate reacts with a carbonyl compound to form an alpha,beta-unsaturated ketone.
A ring formation reaction where a 1,3-dipolar compound reacts with an alkene or alkyne to form a five-membered ring compound.
An aromatic substitution reaction where an aryl diazonium salt reacts with a copper(I) halide or pseudohalide to form an aromatic halide or pseudohalide.
An aromatic substitution reaction where an aryl diazonium salt reacts with copper powder and hydrochloric acid or hydrobromic acid to form an aromatic chloride or bromide.
This is also sometimes known as the Gattermann reaction. Also doesn't work to make fluorides or iodides.
An aromatic substitution reaction where an aryl diazonium salt reacts with a copper(II) halide to form an aromatic halide.
A carbon-carbon coupling reaction where an organohalide or triflate couples to a terminal olefin to produce an internal olefin, catalysed by palladium. It is stereospecific.
This usually produces the trans-olefin rather than the cis-. ALSO Merck Index gives a non-terminal example.
A reaction which preserves the number of rings and number of skeletal atoms and in which the molecule rearranges so that one or more atoms or groups of atoms move from one atom to another.
A rearrangement where an oxime rearranges to form an amide. Often there is selective migration of one group.
A [3,3]-sigmatropic rearrangement where a 1,5-hexadiene rearranges to form a 1,5-hexadiene.
A [3,3]-sigmatropic rearrangement of a 3-hydroxy-1,5-hexadiene rearranges to form a 5,6-unsaturated carbonyl compound.
A joining reaction in which one or more atoms are added to the middle of a chain.
A reaction of a ketone to give an ester, in which an alkyl, benzyl or phenyl group migrates from one of the alpha-carbon centres to an adjacent oxygen, displacing an oxygen-based leaving group; the result is a formal insertion of an oxygen atom. The reaction also works with aldehydes, giving the corresponding carboxylic acid. The term "Baeyer-Villiger rearrangement" may occasionally be used in a mechanistic sense to refer specificially to the actual rearrangement step.
A carbon-carbon coupling reaction where ammonia or an amine reacts with a non-enolisable aldehyde, often methanal, and an enolisable carbonyl compound to form a beta-amino carbonyl compound.
A substitution where an alcohol is converted into something else. Typical reagents are a dialkyl azodicarboxylate and a triarylphosphine. The alcohol stereocentre is inverted.
A carbon-carbon coupling reaction where a stannane reacts with an organohalide or organotriflate.
A carbon-carbon coupling reaction where an aldehyde or amine reacts with a alpha-halo ester and zinc to form a beta-hydroxy ester.
A functional group modification reaction where a functional group is reduced.
A functional group reduction where an aldehyde or ketone carbonyl group is reduced to a methylene with zinc-mercury amalgam and hydrochloric acid.
A joining reaction where a carbon-carbon bond is formed between like moieties.
A carbon-carbon homocoupling reaction of an aryl halide mediated by copper.
A reaction in which two or more groups of atoms are added to the molecule, resulting in a change of skeletal bond order.
Addition of hydrogen atoms to aromatic rings by means of alkali metals in liquid ammonia.
A carbon-carbon coupling reaction of an ester and a carbonyl compound to form a beta-keto ester.
A carbon-carbon coupling reaction of an aldehyde and a methylene compound.
A carbon-carbon coupling reaction between an arene and a carbonyl compound (usually an acyl halide) to give an aryl ketone. The reaction is catalysed by a Lewis acid.
A carbon-carbon coupling reaction between an arene and an alkyl halide/alkene/alcohol (anything that can form a carbocation) to give a substituted arene. The reaction is catalysed by a Lewis acid.
An oxidation of a secondary alcohol to a ketone involving an equilibrium between the alcohol and a reagent ketone present in excess, catalysed by a metal alkoxide.
A carbon-carbon coupling between formaldehyde and an alkene to give a 1,3-diol or an allylic alcohol, catalysed by acid.
See also "intramolecular Prins reaction".
A reaction between formaldehyde and an alkene to give a 1,3-dioxane, catalysed by acid.
A rearrangement of a 1,2-diol to give a carbonyl compound, catalysed by acid.
A rearrangement of a diazoketone to give a ketene, with the elimination of molecular nitrogen.
A reaction in which a fused ring system is present in a product that was not present in any of the reactants.
A cyclodehydration of a beta-phenethylamide to give a 3,4-dihydroisoquinoline.
Bischler-Napieralski 3,4-dihydroisoquinoline synthesis
Bischler-Napieralski dihydroisoquinoline synthesis
Bischler-Napieralski isoquinoline synthesis
A rearrangement of an acyl azide to give an isocyanate by pyrolysis, with the elimination of molecular nitrogen.
A formylation of an activated arene with a disubstituted formamide to give an arenecarbaldehyde.
A carbon-carbon coupling reaction between a phosphonate and a carbonyl compound to give an olefin.
Horner-Wadsworth-Emmons (HWE) olefination
A joining reaction between a phosphine oxide and a carbonyl compound to give an olefin.
A reaction between an alcohol or alkene and a nitrile to give an amide, catalysed by a Bronsted acid.
A condensation-cyclisation of a beta-phenethylamine with an aldehyde to give a tetrahydroisoquinoline.
Pictet-Spengler tetrahydroisoquinoline synthesis
The alkylation of a trialkyl phosphite with an alkyl halide or acyl halide to give an alkyl phosphonate.
An aldol condensation between an aldehyde or ketone and a silyl enol ether (also known as a ketene silyl acetal) to give a beta-hydroxy carbonyl compound.
A condensation between an aromatic amine and glycerol to give a quinoline.
A homologation reaction of a carboxylic acid to give the homologated carboxylic acid via acyl chloride and diazoketone intermediates.
This is an insertion because the carbon atom is added between the R group and the carboxyl carbon in the starting material.
Reaction of an aldehyde or ketone with a phenylhydrazine to give an indole.
An intramolecular cyclisation of a diester to give a cyclic beta-ketoester.
This is the intramolecular version of the Claisen condensation.
A joining of an organic azide and a tertiary phosphine to give a phosphazo compound.
Hydrolysis of the phosphazo compound gives the corresponding amine." [https://orcid.org/0000-0002-4077-4719, RSC:db]
A rearrangement of a hydrazobenzene to give a diaminobiphenyl compound.
A rearrangement of a p-substituted hydrazobenzene to give a p-aminodiphenylamine.
A rearrangement of a heterocyclic compound in which endocyclic and exocyclic heteroatoms swap places.
A molecular skeleton joining reaction in which a chain part of a molecular skeleton is lengthened.
A cleaving reaction in which a peptide is treated with phenylisothiocyanate, removing the terminal amino acid group, to form the chain-shortened amine and a phenylthiohydantoin.
The latter can be used to identify the terminal amino acid, and the process repeated to enable peptide sequencing."
A formylation reaction between a phenol and chloroform (for example, to form an ortho-formyl phenol).
A reaction where atoms are lost from the molecular skeleton.
A carbon-carbon homocoupling reaction of two molecules of an alkyl halide with sodium to give a symmetrical product.
A rearrangement of a 1,2-diketone to an alpha-hydroxy carboxylic acid. It can also be applied to alpha-keto aldehydes. The first exmaple of this reaction was with benzil (PhC(=O)C(=O)Ph) to form benzilic acid, hence the name.
A carbon-carbon coupling of an aldehyde to an activated alkene in the presence of a nucleophilic base to give an alpha-hydroxyalkylated compound.
A coupling of an aldehyde or ketone with an alpha-halo ester to form an alpha,beta-epoxy ester, which hydrolyses to yield aldehydes or ketones by elimination of carbon dioxide.
A reaction in which a functional group is modified by converting it into a protecting group, in order to make subsequent reactions more selective.
A protection reaction in which an amine is converted into a tert-butoxycarbonyl compound.
A carbon-carbon coupling reaction in which an alpha-silyl carbanion reacts with an aldehyde or a ketone to give an alkene, proceeding via a beta-hydroxysilane. The stereochemistry of the alkene can be controlled by treating the intermediate with acid or base.
A coupling reaction in which a phenol is coupled to an aryl halide to give a diaryl ether in the presence of a copper compound.
A coupling reaction in which an acetanilide is coupled to an aryl halide to give an N-acetyl diaryl amine in the presence of a copper compound.
A photochemical cycloaddition between an aldehyde or ketone and an alkene to give an oxetane.
A joining reaction between an aldehyde or ketone and an alkyl halide or aryl halide or vinyl halide or allyl halide in the presence of metal to give a secondary or tertiary alcohol.
A reductive coupling reaction between two esters to give an acyloin (an alpha-hydroxyketone).
A carbon-carbon coupling reaction between a nitroalkane and an aldehyde or ketone to give a beta-hydroxy nitroalkane.
The photolytic oxidation of a nitrate ester to give a gamma-nitroalcohol.
A carbon-carbon coupling reaction between an organohalide or organotriflate and an organozinc compound. The reaction is catalysed by palladium or nickel.
A reduction of an aldehyde or ketone to an alcohol involving an equilibrium between the aldehyde or ketone and a reagent alcohol present in excess, catalysed by a metal alkoxide. This reaction is the reverse of the Oppenauer oxidation (RXNO:0000047).
The reaction between an alkyl halide or alkyl sulfate and a metal alkoxide to give an ether.
A carbon-carbon coupling reaction where a carbonyl compound reacts with a phosphonium ylide to give a terminal alkene.
A Diels-Alder reaction between a diene and an imine or an azadiene and an alkene to give a six-membered nitrogen-containing ring compound.
A cleaving reaction in which a skeletal atom or group of atoms is removed from the middle of a molecule.
The reaction of an alpha-halosulfone to give an alkene, with the extrusion of sulfur dioxide.
The rearrangement of an aromatic nitrosamine to a para-nitrosoaniline.
A coupling reaction of a diazonium salt with a phenol or aniline to give an azo compound.
A carbon-carbon coupling reaction where an imine reacts with a alpha-halo ester and zinc to form a beta-amino ester.
A coupling reaction between two molecules of a terminal alkyne catalysed by Cu(I) salts.
A coupling reaction between two molecules of a terminal alkyne using stoichiometric Cu(II) salts.
A coupling reaction between a terminal alkyne and an alkynyl halide catalysed by Cu(I) salts.
The reductive amination of ketones or aldehydes with an ammonium formate or formamide to form an amine.
The reductive amination of ketones or aldehydes with an amine and formic acid to form amines.
The reaction of primary alkyl halides with sodium or potassium phthalimide, followed by hydrolysis, to give the corresponding primary amine.
The reaction of primary alkyl halides with sodium or potassium phthalimide, followed by treatment with hydrazine, to give the corresponding primary amine.
A reaction in which a single skeletal atom is removed from the end of a chain.
The decarboxylation of silver carboxylates with halogens to give organic halides.
A carbon-carbon coupling reaction between a dialkyl malonate and an alkyl halide, to give a substituted acetic acid. The base/R'X treatment can be repeated to give a disubstituted product.
A reaction in which an existing ring is increased in size.
The reaction between isatin and an alpha-methylene carbonyl compound to give a substituted quinoline-4-carboxylic acid.
A reaction in which the parent molecule breaks up into three or more products.
The fragmentation of a molecule that takes place when an electron-donating fragment (X) and an electron-accepting fragment (X') are situated at positions 1 and 3 on an aliphatic chain, to give a cationic fragment, a neutral fragment (e.g. an alkene) and an anionic fragment.
The rearrangement of an alpha-, beta- or gamma-hydroxy silane to give a silyl ether. It is catalysed by a base.
The reaction of a propargylic cation (stabilised with dicobalt octacarbonyl) with a nucleophile to give a substituted alkyne.
The reaction of a propargylic cation (stabilised with dicobalt octacarbonyl) with a hydride or amine or enamine to give a substituted alkyne.
Nicholas reaction, nucleophilic heteroatom centre
The reaction of a propargylic cation (stabilised with dicobalt octacarbonyl) with a nucleophilic carbon centre (on e.g. enolates, allyl silanes, ketones, electron-rich aromatics, beta-dicarbonyl compounds) to give a substituted alkyne.
Nicholas reaction, nucleophilic carbon centre
A carbon-carbon coupling reaction between a phenyl sulfone and an aldehyde or ketone to give a (typically trans) alkene.
The oxidation of a benzylic halide to give an aldehyde. The reaction uses hexamethylenetetramine.
The reduction of an ester using sodium to give two alcohols.
A base-catalysed isomerisation of a 2,3-epoxyalcohol, with inversion of configuration at C2.
A base-catalysed isomerisation of a 2,3-epoxyamine to form a hydroxy aziridine, with inversion of configuration at C2.
The base-catalysed rearrangement of an o-acetoxyacetophenone to give a hydroxyphenyl-1,3-diketone.
A reaction in which two or more groups of atoms are removed from the molecule, resulting in a change of skeletal bond order.
This is narrower in focus than elimination in general in that we're focussing on the aims of the chemist.
The reaction of a tosylhydrazone of an aldehyde or ketone with a strong base to give an olefin.
This generally provides the more-substituted olefin as the thermodynamic product.
The reaction of a tosylhydrazone of an aldehyde or ketone with an alkyllithium or Grignard reagent to give an olefin.
This generally provides the less-substituted olefin as the kinetic product.
The reaction between an aromatic amine, an aldehyde and pyruvic acid on heating to give a quinoline 4-carboxylic acid (cinchoninic acid).
The conversion of an aromatic amine to the corresponding fluoride via the diazonium fluoroborate.
The decarboxylation and coupling of a carboxylate or mixture of carboxylates to give a dimer.
Reaction of a ketone or aldehyde, amine, an isocyanide and carboxylic acid to form a bisamide.
The oxidation of a terminal alkene or ethene to a methyl ketone or acetaldehyde, catalysed by PdCl2 and CuCl2, and using molecular oxygen as the oxidant.
The oxidation of ethene to acetaldehyde, catalysed by PdCl2 and CuCl2, and using molecular oxygen as the oxidant.
The reaction of carbon monoxide with methanol to form acetic acid, catalysed by a rhodium complex.
The reaction of carbon monoxide with methanol to form acetic acid, catalysed by an iridium complex.
The deoxygenation of an alcohol to the corresponding alkane using a thiochloroformate. It proceeds by a radical mechanism.
The decarboxylation of a carboxylic acid to the lower homologue alkane using a pyridine thione.
The reaction proceeds by a radical mechanism.
The hydrogenolysis of an acyl halide to the corresponding aldehyde, catalysed by palladium-on-barium sulfate.
A carbon-carbon coupling reaction where a terminal alkyne reacts with an aryl halide to give an aryl alkyne. It is catalysed by palladium.
A reaction between two aromatic aldehydes to give a benzoin (an alpha-hydroxyketone).
The formylation of an arene with hydrogen cyanide to give an aryl aldehyde or ketone.
This is essentially a variant of the Friedel-Crafts acylation.
The coupling of a boronic acid or boronic ester with an unsaturated halide, triflate or sulfonate catalysed by a palladium(0) complex.
The epoxidation of an allylic alcohol to give a beta,gamma-epoxy alcohol, with control of absolute stereochemistry at the two new stereocentres. The oxidising agent is tert-butyl hydroperoxide, and the catalyst is a complex of titanium salt and optically active diethyl tartrate.
Katsuki-Sharpless asymmetric epoxidation
Sharpless-Katsuki asymmetric epoxidation
The dihydroxylation of an alkene to give an alpha,beta-diol, with control of absolute stereochemistry at the two new stereocentres. The oxidising agent is osmium tetroxide, which is used catalytically with a stoichiometric oxidant and a chiral ligand. The reagents are available commercially as AD-mix.
The aminohydroxylation of an alkene to give a beta-amino alcohol, with control of absolute stereochemistry at the two new stereocentres. The oxidising agent is an oxygen-containing osmium species and/or an amino derivative which can be used catalytically with a stoichiometric oxidant and a chiral ligand.
A cross-coupling reaction between a Grignard reagent and an activated (aryl or vinyl) halide or triflate. The reaction is catalysed by a palladium or nickel catalyst.
The degradation of a carboxylic acid to its next lower homologous carboxylic acid.
A homologation reaction of an aldehyde to yield a terminal alkyne. The reagents are tetrabromomethane, triphenylphosphine, butyllithium and water.
A reduction of a quaternary ammonium salt containing at least one unsaturated substituent, to give a tertiary amine.
The [3,3]-sigmatropic rearrangement of an allyl vinyl ether to give a gamma,delta-unsaturated carbonyl compound.
The enolisation and subsequent [3,3]-sigmatropic rearrangement of an allylic acetate to give a gamma,delta-unsaturated carboxylic acid.
A reaction in which one or more atoms are added to the molecular skeleton and a skeletal rearrangement occurs.
The coupling and subsequent [3,3]-sigmatropic rearrangement of an allylic ether or allylic thioether or allylic amine and a ketene to give the corresponding gamma,delta-unsaturated carbonyl compound.
The coupling and subsequent [3,3]-sigmatropic rearrangement of an allylic alcohol and alpha,alpha-dialkoxy ethylamine to give a gamma,delta-unsaturated dialkyl amide.
The coupling and subsequent [3,3]-sigmatropic rearrangement of an allylic alcohol and trimethyl orthoacetate to give a gamma,delta-unsaturated alkyl ester.
The oxidation of a primary alcohol or secondary alcohol to an aldehyde or ketone respectively. Does not work with allylic or benzylic alcohols.
The conversion of an alkyl chloride, alkyl bromide or alkyl sulfonate ester to an alkyl iodide by SN2 substitution. The reaction relies upon the equilibrium being pushed to completion by the precipitation.
The derivatisation (for example with tosyl chloride) and subsequent rearrangement of a hydroxamic acid to give an isocyanate.
The conversion of a primary nitroalkane or secondary nitroalkane to an aldehyde or ketone, respectively.
The reaction of a doubly activated methylene compound that has at least one carbonyl substituent with an aryl azide to give a hydrazone. Usually there is concomitant cleaving and oxidation of one of the carbonyl substituents.
The formation of a quinoline from a primary aromatic amine and an alpha,beta-unsaturated carbonyl compound.
Skraup-Doebner-von Miller quinoline synthesis
The protection of an amine (often a peptide) as its 9H-fluoren-9-ylmethoxycarbonyl derivative.
The cyclisation of a 1,4-dicarbonyl compound with another molecule to give a five-membered aromatic ring compound.
Usually this gives rise to a heterocycle.
The cyclisation of a 1,4-dicarbonyl compound with an acid catalyst to give a furan.
The cyclisation of a 1,4-dicarbonyl compound with phosphorus pentasulfide to give a thiophene.
The cyclisation of a 1,4-dicarbonyl compound with an amine to give a pyrrole.
Merck Index says "ammonia or primary amines"
The coupling of an alcohol or amine with an acyl chloride to give an ester or amide. A two-phase solvent system is often used, to enable the acid generated during the reaction to be neutralised by the aqueous base, while the starting materials and products remain in the organic phase.
The elimination of a methylated amine from an alkylamine to form an olefin. The reaction proceeds via the quaternary ammonium salt.
The esterification of a carboxylic acid with an alcohol. Various Lewis acids or Bronsted acids may be used as catalyst.
The degradation of an alpha-hydroxy amide or an alpha,beta-unsaturated amide to the lower homologue aldehyde, especially in carbohydrate chemistry. The process proceeds via Hofmann degradation.
The reaction of ortho- or para-phenolic (or ortho- or para-anilinic) aldehydes or ketones with hydrogen peroxide to form bisphenols (or hydroxy anilines) and carboxylic acids.
The reaction of a carboxylic acid with hydrazoic acid to give the lower homologue amine, with the loss of the terminal carbon atom.
The reaction of a ketone with hydrazoic acid with the insertion of an NH group between the carbonyl carbon and one of the R groups to form an amide.
The reaction of a tertiary alcohol with hydrazoic acid with rearrangement to form an imide.
The reaction of an alkene with hydrazoic acid with rearrangement to form an imide.
The [2,3]-sigmatropic rearrangement of a benzyl quaternary ammonium salt to form an aniline.
The reaction of an amino acid with an acid anhydride to give an alpha-acylamido ketone. The reaction proceeds via the mixed anhydride and an oxazolone; the product is always racemic.
The cleavage of an oxime to the corresponding nitrile and an alkyl halide. This reaction is related to the Beckmann rearrangement, and occurs when the R group that is anti to the oxime hydroxyl is quaternary.
The transfer of a hydrogen or halogen atom from a haloalkane to an alkene, giving the chain-extended halogenated alkane.
The allylic oxidation of an alkene with a peroxy ester or a peroxide to give the corresponding allylic alcohol derivative. The catalyst is a copper compound.
The oxidation of a phenol to give a (predominantly para) diphenol using potassium persulfate.
Elbs persulfate oxidation, phenol variant
The oxidation of a methyl-substituted aromatic compound to the corresponding benzaldehyde using potassium persulfate.
Elbs persulfate oxidation, tolyl variant
The oxidation of an aromatic amine to give a (predominantly ortho) amino aryl sulfate using potassium persulfate followed by hydrolysis to yield the corresponding aminophenol.
The (predominantly ortho) carboxylation of a phenoxide.
The reaction between an alpha-halocarbonyl compound and a trialkyl phosphite to give an enol phosphate.
not clear why this is where it is and not a sibling of the Arbuzov reaction (2014-02-17)
The oxidation of a primary or secondary alcohol to the corresponding aldehyde or ketone respectively using dimethyl sulfoxide, 1,3-dicyclohexylcarbodiimide and acid. The reaction proceeds via an alkoxysulfonium ylide.
The conversion of an aryl alkyl ketone to an amide and/or an ammonium salt of a carboxylic acid using ammonium polysulfide. The carbonyl group of the product is always at the end of the alkyl chain.
The conversion of an aryl alkyl ketone to an amide using sulfur and dry ammonia or a primary or secondary amine. The amide carbonyl group is always at the end of the alkyl chain.
The formation of an ester from two aldehydes via a disproportionation process using a metal alkoxide to oxidise one aldehyde and reduce the other.
The reaction between a methylene ketone and a polynitro aromatic compound.
The rearrangement of the sulfonic ester of a ketoxime in base to give an alpha-amino ketone.
A coupling reaction of an aldehyde to an allyl, vinyl or aryl halide or triflate in the presence of chromium(II). It is catalysed by nickel.
A reaction in which an aryl halide or aryl triflate reacts with a primary or secondary amine in the presence of base to give a secondary or tertiary amine. It is catalysed by a palladium catalyst.
A carbon-carbon coupling reaction where an organosilane reacts with an organic halide or triflate. It is catalysed by a palladium or nickel complex.
The 1,2-rearrangement of an alpha-methylene ammonium salt or alpha-methylene sulfonium salt to an amine or sulfide in the presence of strong base.
The 1,2-rearrangement of an alpha-methylene ammonium salt to an amine in the presence of strong base.
The 1,2-rearrangement of an alpha-methylene sulfonium salt to a sulfide in the presence of strong base.
A [3,3]-sigmatropic rearrangement where an aza-1,5-hexadiene rearranges to form an aza-1,5-hexadiene.
The rearrangement of a 2-aza-1,5-hexadiene to form an imine.
The rearrangement of a 3-aza-1,5-hexadiene to form a delta,epsilon-unsaturated imine.
This is the reverse of the 1-aza-Cope rearrangement.
The rearrangement of a delta,epsilon-unsaturated imine to form a 3-aza-1,5-hexadiene.
This is the reverse of the 3-aza-Cope rearrangement.
The rearrangement of an oxazolyl carbonate to a C-carboxyazlactone.
A reaction in which the number of rings in a molecule stays the same but the connectivity of the atoms in at least one ring changes.
A reaction in which a protecting group is modified by converting it into a functional group.
A joining reaction in which two carbon-carbon multiple bonds are redistributed among two fragments. The reaction is typically catalysed by a metal carbenoid, and proceeds via two four-membered intermediates (metallacyclobutanes). The reaction is driven by release of a low-MW alkene.
A planned reaction step in which the product has fewer rings than the reactants.
A planned reaction step in which an existing ring is reduced in size.
An addition reaction between a carbonyl compound, an inorganic cyanide and an ammonium salt, followed by hydrolysis, to give an alpha-amino carboxylic acid.
The [3,3]-sigmatropic rearrangement, and subsequent re-aromatisation, of an allyl aryl ether to give an ortho-allyl phenol.
The acid-catalysed cyclisation of a divinylketone to give a cyclopentenone.
The stereospecific oxidation of a (phenyldimethylsilyl)alkane to the corresponding alcohol using bromine, usually generated in situ from potassium bromide and peracetic acid.
The stereospecific oxidation of a (halosilyl)alkane to the corresponding alcohol using potassium fluoride and hydrogen peroxide.
A carbon-carbon coupling reaction in which an aldehyde or ketone reacts with allyltrimethylsilane to form a homoallylic alcohol.
A carbon-carbon coupling reaction in which an enone reacts with allyltrimethylsilane to form a delta,epsilon-unsaturated carbonyl compound.
A carbon-carbon coupling reaction in which an acid chloride reacts with allyltrimethylsilane to form a gamma,delta-unsaturated ketone.
A carbon-carbon coupling reaction in which an acetal or ketal reacts with allyltrimethylsilane to form a homoallylic ether.
A carbon-carbon coupling reaction in which an imine reacts with allyltrimethylsilane to form a homoallylic amine.
A ring-breaking reaction in which an epoxide reacts with allyltrimethylsilane to form a hydroxy alkene.
The disproportionation of a non-enolisable aldehyde to the corresponding carboxylic acid and alcohol. The reaction is base-catalysed.
The reaction between two different non-enolisable aldehydes to give a carboxylic acid and an alcohol. The reaction is base-catalysed.
The conversion of a sulfoxide with an alpha-hydrogen to an alpha-substituted thioether. The reaction is usually performed with an acid anhydride or acyl halide.
The reaction of a tertiary amine oxide with an anhydride or acyl chloride to give an N,N-disubstituted acetamide and an aldehyde.
The reaction of a tertiary amine oxide with trifluoroacetic anhydride to give an N,N-disubstituted acetamide and an aldehyde.
The alkylation of a tertiary amine with an alkyl halide to the corresponding ammonium salt.
The deamination and decarboxylation of amino acids to imines and then to aldehydes or ketones, in the presence of a carbonyl compound (especially an alpha,beta-dicarbonyl compound or a reducing sugar such as glucose). The reaction is involved in the generation of meat aromas/flavours in cooking.
The allylic or benzylic bromination of hydrocarbons using an N-bromoimide and a radical initiator, to give an allylic or benzylic bromide.
The reduction of an aldehyde or ketone to the corresponding methylene compound, using hydrazine hydrate and a base.
The reduction of an aldehyde or ketone to the corresponding methylene compound, using hydrazine hydrate and a base in refluxing ethylene glycol.
Wolff-Kishner reduction, Huang-Minlon modification
The reduction of an ester to the corresponding alcohol, using sodium methoxide in dry methanol.
The rearrangement of an O-alkenyl acetal to give the corresponding beta-alkoxy carbonyl compound.
The rearrangement of an O-alkenyl hemiaminal ether to give the corresponding beta-amino carbonyl compound.
A joining reaction where an N=C system with an allylic hydrogen reacts with a compound containing a multiple bond (an enophile) to form a substituted alkene.
The alkylation of an amine with a boronic acid and an aldehyde to give a substituted amine.
A rearrangement of a furfuryl alcohol derivative to a dihydropyranone, from which monosaccharides may be synthesised.
A rearrangement of a furfuryl amine derivative to a tetrahydropyridinone.
A carbon-carbon coupling reaction between a nitroalkane and an imine to give a beta-amino nitroalkane.
A three-component coupling of a beta-keto ester, an aldehyde and urea to give a 3,4-dihydropyrimidinone.
The coupling of an alpha-bromo ester with a nitrile to give a beta-ketoester, in the presence of zinc.
The substitution of an amine with a nucleophile using a pyrylium salt.
The rearrangement of a 3-aza-4-metalla-1,5-hexadiene to form a delta,epsilon-unsaturated metallaimine.
The cyclisation of an ene-diyne to give a 1,4-diradical cyclohexatriene. The diradical usually aromatises.
A conjugate addition reaction where a carbon nucleophile adds to an alpha,beta-unsaturated nitro compound.
The homogeneous asymmetric catalytic hydrogenation of a C=C double bond using a ruthenium(II) BINAP catalyst.
The homogeneous asymmetric catalytic hydrogenation of a carbonyl bond using a ruthenium(II) BINAP catalyst.
Noyori asymmetric hydrogenation, carbonyl
The reaction between an isonitrile, a carboxylic acid and aldehyde or ketone to give an alpha-acyloxy amide.
A joining reaction in which two carbon-carbon double bonds in the same molecule are redistributed to give a cycloalkene. It is typically catalysed by a metal carbenoid, and proceeds via two four-membered intermediates (metallacyclobutanes). The reaction is driven by release of a low-MW alkene.
A joining reaction, the objective of which is that a large number of monomers react together to produce a polymer consisting of repeating units.
A joining reaction in which two carbon-carbon double bonds are redistributed among two fragments, i.e. two alkenes. It is typically catalysed by a metal carbenoid, and proceeds via two four-membered intermediates (metallacyclobutanes). The reaction is driven by release of ring strain in the cycloalkene.
An adaptation of the Claisen rearrangement that transforms a beta-keto allyl ester into a gamma,delta-allyl ketone. It uses base and high temperature or milder conditions with a ruthenium or palladium complex as catalyst.
A Mitsunobu reaction, where an alcohol is converted to something else with inversion at the stereocentre, using diphenylphosphoryl azide.
The rearrangement of a 2-bromoalkene into an alkyne, mediated by strong base.
Fritsch-Buttenberg-Wiechell rearrangement
A carbon-carbon coupling reaction where an aldehyde reacts with a phosphonium salt to give a Z-iodoalkene. The reaction is mediated by sodium or potassium hexamethyldisilazide.
The reduction of a 2-nitrobiaryl compound to give a carbazole.
The arylation of an arylamine mediated by isopentyl nitrite.
The reaction between a 1,9-diformyldipyrromethane and a dipyrromethane to give a porphodimethene.
The carbon-carbon homocoupling reaction of a pair of alkyne molecules using a borane and iodine. The reaction proceeds via a borane intermediate.
The oxidation of a primary alcohol to an aldehyde or a secondary alcohol to a ketone using the Dess-Martin periodinane.
The oxidative cleavage of an alpha,beta-diol using lead tetraacetate to give the corresponding carbonyl compounds.
A ring formation reaction where an alkene reacts with a dihalomethane in the presence of a metal atom or metal complexes to form a cyclopropane. The traditional reaction uses a zinc-copper couple and diiodomethane.
Any of a family of sigmatropic rearrangements that involve the migration of a group on an electronegative atom (O or N) to a carbon atom.
A base-mediated 1,2-sigmatropic rearrangement of an ether to give an alcohol.
A base-mediated 2,3-sigmatropic rearrangement of an allyl ether to give a homoallylic alcohol.
A base-mediated 1,2-sigmatropic rearrangement of a tertiary amine to give a secondary amine.
A base-mediated 2,3-sigmatropic rearrangement of an activated tertiary allyl amine, to give a secondary homoallylic amine.
A carbon-carbon coupling of an imine to an activated alkene in the presence of a nucleophilic base to give an allylic amine.
Reaction of a carbonyl compound with a phosphazene to give an imine.
An oxidation reaction involving Fenton's reagent.
A ring-forming reaction between two equivalents of a beta-ketoester, an aldehyde and ammonia (or an ammonium salt), to give a dihydropyridine. The dihydropyridine can be oxidised to a pyridine using an oxidising agent.
A [3+2] cycloaddition reaction between an azide and an alkyne to give a 1,2,3-triazole, needing only heat to proceed.
Note: The term "click reaction" was originally used in a broader sense to refer to any coupling that took place cleanly and quickly in quantitative yield, but it now always seems to be used in this narrower sense.
A [3+2] cycloaddition reaction between an azide and an alkyne to give a 1,2,3-triazole as a single regioisomer.
copper(I)-catalysed alkyne-azide cycloaddition
copper(I)-catalysed azide-alkyne click reaction
copper(I)-catalysed azide-alkyne cycloaddition
copper(I)-catalyzed alkyne-azide cycloaddition
copper(I)-catalyzed azide-alkyne click reaction
copper(I)-catalyzed azide-alkyne cycloaddition
Commonly described as a variant of the (uncatalyzed) alkyne-azide click reaction, the mechanism of reaction is different, and thus formally it is not a 1,3-dipolar cycloaddition. [rsc:db]
A process in which carbon monoxide and hydrogen ('syngas') are converted into various liquid hydrocarbons.
The reaction of hydrogen and carbon monoxide with an alkene, to give an aldehyde, catalysed by a rhodium or cobalt catalyst. The process is equivalent to the formal addition of the H-C bond of formaldehyde across the double bond of an alkene.
The reverse of a [4+2] cycloaddition reaction, in which an unsaturated six-membered ring compound fragments to give a diene and a compound containing a double or triple bond (a dienophile).
The reverse of an aldol addition, in which a beta-hydroxy ketone fragments to form a carbonyl compound and the enolate of an alpha-acidic carbonyl compound.
This process can occur because the whole reaction is an equilibrium. In the forward direction (aldol addition), elimination of water from the beta-hydroxy ketone, giving an alpha,beta-unsaturated ketone, is irreversible, and thus the aldol condensation does not have a "retro" counterpart.
A hydrogenation in which a metal-ligating group distant from the reacting alkene directs the attack of hydrogen, giving preferentially one stereoisomer of the product.
The insertion of alkenes (usually ethene) into the Al-C bond of an aluminium alkyl, to give a long-chain aluminium alkyl that can go on to react again, or can decompose into the corresponding terminal alkene. The addition of transition metals results in reliable production of high molecular weight polymers.
The reaction of an aluminium alkyl with an alkene, to give an intermediate aluminium species that can give various products after work-up.
The reaction of two alkenes to give an elongated alkene, employing a transition-metal-based catalyst.
The reaction of a 1,3-diene with an alkene to give a 1,4-diene, usually employing a cobalt-based catalyst (see Hilt and Luers, Synthesis, 2002, 609).
A joining reaction in which two carbon-carbon double bonds are redistributed among two fragments, i.e. two alkenes. It is typically catalysed by a metal carbenoid, and proceeds via two four-membered intermediates (metallacyclobutanes). The reaction is driven by release of a low-MW alkene.
A joining reaction in which two carbon-carbon triple bonds are redistributed among two fragments, i.e. two alkynes. It is catalysed by a metal carbenoid, and proceeds via two four-membered intermediates (metallacyclobutenes). The reaction is driven by release of a low-MW alkyne.
A joining reaction in which a carbon-carbon double bond and a carbon-carbon triple bond are redistributed among two fragments, i.e. an alkene and an alkyne. It is typically catalysed by a metal carbenoid, and proceeds via two four-membered intermediates (metallacyclobutenes). As a low-MW alkene is not released, the reaction is usually driven by formation of a ring.
A joining reaction in which a carbon-carbon double bond and a carbon-carbon triple bond in the same molecule are redistributed to give a alkene-substituted cycloalkene. It is typically catalysed by a metal carbenoid, and proceeds via two four-membered intermediates (metallacyclobutanes). The reaction is driven by formation of the ring.
A ring-breaking reaction in which two carbon-carbon double bonds are redistributed among two fragments, i.e. an alkene and a cycloalkene. It is typically catalysed by a metal carbenoid, and proceeds via two four-membered intermediates (metallacyclobutanes). The reaction is driven by release of ring strain in the cycloalkene.
A carbon-carbon coupling reaction where an aldehyde or ketone reacts with an allyl halide and zinc to give a homoallylic alcohol.
Not to be confused with the Luche reduction (the chemoselective reduction of an enone to an allylic alcohol).
The chemoselective reduction of an enone to give an allylic alcohol, using sodium borohydride and an lanthanoid chloride, typically cerium chloride.
Not to be confused with the Luche reaction (the coupling of an aldehyde or ketone with an allyl halide).
The oxidation of an aldehyde to a carboxylic acid with chlorite.
A carbon-carbon coupling reaction where an aryl halide reacts with copper(I) cyanide to give an aryl nitrile.
The formation of urea from ammonium cyanate. Ammonium cyanate is unstable, and so is formed in situ from either (a) cyanic acid and ammonia, (b) a metal cyanate and an ammonium salt, or (c) a metal cyanate and ammonia.
The addition of a hydrosilane across the double bond of an alkene or alkyne to give a more substituted silane. Addition to an aldehyde or ketone produces a silyl ether.
The addition of the N-H bond of an amine across a double bond of an alkene or alkyne, to give a more substituted amine.
The addition of a boron hydride across a double bond of an alkene or alkyne. The boron usually adds to the less substituted carbon.
The formal addition of water across a double bond of an alkene or alkyne by formation of an organoborane and in situ oxidation, typically with basic peroxide. The product is usually the less substituted alcohol.
The reaction of any of a number of metal hydride species with an alkene or alkyne, to give an intermediate organometal species that can give various products after work-up.
The reaction of a organozirconium hydride with an alkene or alkyne, to give an intermediate zirconium species that can give various products after work-up. The zirconium reagent used is typically Schwartz's reagent, Cp2ZrHCl.
The reaction of a organotin hydride with an alkene or alkyne, to give an intermediate tin species that can give various products after work-up.
The reaction of a organotellurium hydride with an alkyne, to give a (usually (Z)-configured) vinyltellurium species.
The oxidation of a primary alcohol to an aldehyde or a secondary alcohol to a ketone using Fetizon's reagent.
The substitution of an acylated sugar with a silylated base to give a nucleoside.
The addition of a thiol across the double bond of an alkene to give a thioether.
The nickel-catalysed carbon-carbon coupling of a dihaloaromatic compound or aromatic bistriflate to give a polymer.
The thermally induced addition of a hydrosilane across the double bond of an alkene or alkyne to give a more substituted silane, usually applied to cases where the hydrosilane is part of a silicon surface.
The photochemically induced addition of a hydrosilane across the double bond of an alkene or alkyne to give a more substituted silane, usually applied to cases where the hydrosilane is part of a silicon surface. The reaction uses UV irradiation and is usually initiated by an added photoactive compound such as a platinum catalyst.
A carbon-carbon coupling reaction between a tetrazole sulfone and an aldehyde or ketone to give a (typically trans) alkene.
The conversion of a selenoxide with an alpha-hydrogen to an alpha-subtituted selenoether.
A carbon-carbon coupling reaction where an organohalide or triflate couples to an alkene in the same molecule, catalysed by palladium.
An intramolecular Heck reaction of an ortho-halo-aniline with an alkene, catalysed by palladium.
The intramolecular esterification of a carboxylic acid group with an alcohol group using 2,4,6-trichlorobenzoyl chloride (Yamaguchi reagent) - an intramolecular Yamaguchi esterification.
The esterification of a carboxylic acid with an alcohol using 2,4,6-trichlorobenzoyl chloride (Yamaguchi reagent).
A Diels-Alder reaction between a diene and an aldehyde or ketone to give a six-membered oxygen-containing ring compound.
A carbon-carbon coupling reaction in which a nucleophile reacts with an allyl acetate, allyl halide, allyl carbonate, allyl carbamate, allyl phosphate, allyl sulfone or allyl nitro compound to give an allyl compound. The reaction is catalsed by Pd(0).
A ring rearrangement reaction where an amine reacts with a 2,5-dialkoxytetrahydrofuran to give a pyrrole.
A [4+2] cycloaddition reaction where a diene (or heterocyclic analogue) reacts with a dienophile to form an unsaturated heterocyclic six-membered ring compound.
A carbon-carbon coupling reaction that is catalysed by a palladium atom.
palladium-catalysed carbon-carbon coupling reaction
A condensation reaction that results in the production of an ester.
A deprotection reaction where the reactive centre is an amino nitrogen atom.
A protection reaction where the reactive centre is an amino nitrogen atom.
An amino group protection where the amino nitrogen atom is protected by reaction with benzylamine.
A protection reaction where the reactive centre is a hydroxyl oxygen atom.
A hydroxyl group protection where the hydroxyl oxygen atom is protected by formation of a benzyl ether.
A protection reaction where the reactive centre is a carboxy oxygen.
An amino group deprotection reaction where a tertbutoxycarbonyl group is removed in acid conditions.
An amino group deprotection reaction where a benzylamine group is removed by hydrogenation.
A hydroxyl group protection where the hydroxyl oxygen atom is protected by formation of a silyl ether.
An experimental procedure with the aim of producing a portion of a given compound or mixture.
A hydroxyl group protection where the hydroxyl oxygen atom is protected by formation of an acetate ester.
A functional modification step in which one singly-bonded substituent, but not a hydrogen, is replaced by another singly-bonded substituent.
A substitution step where one singly-bonded substituent on an aromatic skeleton is replaced by another singly-bonded substituent.
An aromatic substitution reaction where an aryl diazonium salt reacts with a copper(I) halide to form an aromatic halide.
An aromatic substitution reaction where an aryl diazonium salt reacts with a copper(II) pseudohalide to form an aromatic pseudohalide.
A functional group modification where a carbonyl oxygen is replaced by an amine.
A reduction reaction where a nitro group is reduced to an amino group.
A reduction process where an amide is transformed into an amine.
A hydrogenation reaction where an alkene is reduced to an alkane.
An N-alkylation where the reactive centre is an amide nitrogen.
An N-alkylation where the reactive centre is an aniline nitrogen.
A reduction where a nitrile is replaced by an amine function.
A reduction reaction where an imine function is replaced by an amine.
An alkene oxidation where the carbon-carbon double bond is cleaved.
An N-alkylation reaction where the reactive centre is an azacycle ring nitrogen.
A ring formation reaction where the intended product contains an oxacycle that was not in any of the reactants.
A ring formation reaction where the intended product contains an azacycle that was not in any of the reactants.
A ring formation reaction where the intended product contains an thiacycle that was not in any of the reactants.
A ring formation reaction where the intended product contains a heterocycle that was not in any of the reactants.
A hydrogenation reaction where an alkyne is reduced to an alkane.
A hydrogenation reaction where an aryl ring is reduced to a cycloalkyl ring.
A hydrogenation reaction where a heteroaryl is reduced to a saturated heterocycle.
heteroaryl reduction to saturated heterocycle
An alcohol oxidation where the alcohol centre is replaced with a carboxy group.
An oxidation reaction where a carbon centre bonded to the benzene ring is oxidized to a carboxyl group.
An oxidation reaction where an allylic C-H bond is replaced by a C=O bond.
This can be done with, for instance, selenium dioxide.
An oxidation reaction where an alcohol is oxidized to the corresponding carbonyl compound by a dichromate ion.
An acylation reaction where a nitrogen atom is acylated to form an amide.
An acylation reaction where a nitrogen atom is acylated to form a urea.
An N-acylation reaction where a nitrogen centre is acylated to form a carbamate.
An O-acylation reaction where an oxygen centre is acylated to result in an ester.
A functional group modification where a nitrile reacts with an alcohol under acid catalysis to form an amidine or ester.
An oxidation reaction where a nitrile reacts with an alcohol to form an alkyl imidate.
A functional group modification where an amide is converted to an imidoyl chloride.
A functional group modification where an alcohol is converted to a halide.
A functional group modification where a carboxylic acid is converted to an acid chloride.
carboxylic acid to acid chloride conversion
A functional group modification where a nitrile is transformed into a carboxylic acid.
A functional group modification where a carbonyl compound is converted to an imine.
Oxidation of an alkene to an allene by heating with formaldehyde, an amine and an inorganic salt.
A carbon-carbon coupling reaction between an arene and a carbonyl compound (an acylation) or an alkyl compound that can form a carbocation (an alkylation) to form a substituted arene.
A functional group modification of a nitrile to a 1H-tetrazole by addition of sodium azide.
A diazotisation that proceeds by the addition of nitrous acid, nitric acid and water, resulting in a diazonium nitrate salt.
An N-arylation reaction where the reactive centre is an azacycle ring nitrogen.
A planned reaction step in which a covalent bond is formed between the molecular skeleton and a functional group and where the skeletal bond order is unchanged.
this is not part of David's grand diagram - well spotted Roger
Arylation of an amine or an alcohol with an arylboronic acid, stannane or siloxane in air with a copper acetate catalyst.
The canonical variant is the N-arylation of an amine with an arylboronic acid.
N-methylation of a primary or secondary amine with formic acid and formaldehyde to yield a tertiary amine.
Coupling of two aromatic rings in the presence of a Lewis acid catalyst.
Scholl reaction within a single molecule to form a larger ring system.
Scholl reaction between two aromatic molecules to form a single molecule.
Reaction of a cyclohexanone with methyl vinyl ketone to form a fused-ring cyclohexenone. It is a Michael reaction followed by an intramolecular aldol condensation.
Rearrangement of a beta-amino alcohol to yield a carbonyl compound. In the first step the amine is diazotised by reaction with nitrous acid.
Substitution reaction of a primary amine via deazotisation to yield a mixture of the corresponding primary alcohol and secondary alcohol.
TODO: Not *entirely* sure how we classify this. Have given it multiple parentage for the now.
Reaction of an thiol with an alkyne to form an alkenyl sulfide.
thiol-yne reaction
Base-catalysed rearrangement of a cyclic alpha-haloketone to the ring-contracted cyclic carboxylic acid.
cyclic alpha-haloketone Favorskii rearrangement
Base-catalysed rearrangement of an alpha-haloketone to a carboxylic acid or ester or amide.
Favorskii rearrangement of a cyclic alpha-dibromoketone followed by decarboxylation to yield a ring-contracted cyclic ketone.
Reaction of a carbonyl compound with a dimethyl diazomethyl phosphonate under basic conditions to yield an alkyne.
Reaction of an aldehyde with a dimethyl diazomethyl phosphonate under basic conditions to yield a terminal alkyne.
Reaction of a ketone with a dimethyl diazomethyl phosphonate under basic conditions to yield a terminal alkyne.
Seyferth-Gilbert aldehyde homologation where the Seyferth-Gilbert reagent is generated in situ by reaction with methanol and potassium carbonate.
Synthesis of a pyrazole by condensation of a 1,3-dicarbonyl compound with a hydrazine, hydrazide, semicarbazide or aminoguanidine.
A reaction in which the intended product is a pyrazole that was not present in any of the reactants.
A reaction in which the intended product is a quinoline that was not present in any of the reactants.
Synthesis of an alpha-hydroxyquinoline by reaction of a beta-ketoester and an arylamine then dehydration with concentrated sulfuric acid.
A reaction in which the intended product is an indole that was not present in any of the reactants.
Palladium-catalysed synthesis of a 2,3-substituted indole by reaction of an ortho-iodoaniline with an internal alkyne.
Reaction of an organic diazo compound with an acetylene to yield a pyrazole.
A reaction in which the intended product is a benzimidazole that was not present in any of the reactants.
Reaction of an ortho-diaminobenzene with a carboxylic acid under heat to yield a benzimidazole.
This may be done in the presence of an acid, hexamethyldisilazane in the presence of catalytic triflic acid, a titanium catalyst, elevated pressure, or under UV. [ISBN:9780080534459]
A reaction in which the intended product is a pyrimidine that was not present in any of the reactants.
A reaction in which the intended product is a triazine that was not present in any of the reactants.
Reaction of a 1,3-dicarbonyl compound with an amidine to yield a pyrimidine.
Reaction of aryl amidines or halogenated aliphatics amidines with phosgene to yield a 2-hydroxy-4,6-diaryl-s-triazine with loss of ammonia.
Cyclisation-condensation of a beta-arylethanol with an aldehyde to yield an ortho,peri-fused aryl-oxacycle.
Epoxidation of an alkene by reaction with a peroxy acid.
Conversion of an alcohol to an alkyl halide with triphenylphosphine and a halide source.
Conversion of an alcohol to an alkyl iodide with triphenylphosphine and tetraiodomethane.
Conversion of an alcohol to an alkyl chloride with triphenylphosphine and tetrachloromethane.
Conversion of an alcohol to an alkyl bromide with triphenylphosphine and tetrabromomethane or bromine.
Rearrangement of a primary carboxylic amide to an isocyanate.
This counts as an end-of-chain chain shortening because the terminal carbon is separated from the skeleton into the isocyanate group.
Conversion of a primary carboxylic amide to the lower homologue primary amine. The first step is the Hofmann rearrangement
Rearrangement of an O-aryl thiocarbamate to an S-aryl thiocarbamate by migration of the aryl group.
Substitution of phenol ortho- or para-bromo or iodo groups by a nitro group on treatment with nitrous acid or a nitrite in acetic acid.
A coupling of an aldehyde with an alpha-haloethanoate ester to form the next homologous aldehyde.
These are not necessary-and-sufficient conditions because we can't say "one longer" in OWL.
haloethanoate ester-aldehyde Darzens reaction
A coupling of a ketone with an alpha-haloethanoate ester to replace the oxo group with a formyl group.
haloethanoate ester-ketone Darzens reaction
Protection of a primary amino group by reaction with phthalic anhydride.
Conversion of a phthalimide into the corresponding primary amine.
Condensation of a 1,5-diketone with ammonium acetate in acetic acid to form a pyridine.
A Gattermann halogenation where the aryl diazonium salt reacts with copper powder and hydrochloric acid to yield an aromatic chloride.
A Gattermann halogenation where the aryl diazonium salt reacts with copper powder and hydrobromic acid to yield an aromatic bromide.
A joining reaction between an aldehyde and an alkyl halide or aryl halide or vinyl halide or allyl halide in the presence of metal to give a secondary alcohol.
A joining reaction between an ketone and an alkyl halide or aryl halide or vinyl halide or allyl halide in the presence of metal to give a tertiary alcohol.
Protection of a hydroxy group by reaction with pivaloyl chloride, resulting in formation of a pivaloyl ester.
A hydroxy group deprotection where a pivalate group is removed in acid or base conditions.
A deprotection reaction where the reactive centre is an oxygen atom.
A carboxylic acid reduction where the product is the corresponding primary alcohol.
carboxylic acid to primary alcohol reduction
A carboxy group protection where the product is a tert-butyl ester.
A deprotection reaction where the reactive centre is a carboxy oxygen atom.
A deprotection reaction where the reactant is a tert-butyl ester and the product is a carboxylic acid.
A deprotection reaction where the reactant is a methyl ester and the product is a carboxylic acid.
A deprotection reaction where the reactant is an ethyl ester and the product is a carboxylic acid.
An objective specification that describes how a molecule's skeleton and substituents are to be transformed by a given experiment.
A molecular transformation specification that specifies that atoms should be lost from the molecular skeleton.
A molecular transformation specification that specifies that the product should contain a ring that was not in any of the reactants.
A molecular transformation specification that specifies that atoms should be added to the molecular skeleton.
A molecular transformation specification that specifies that the number of rings and number of skeletal atoms should be preserved and that one or more atoms or groups of atoms move from one atom to another.
A molecular transformation specification that specifies that the substituents of a molecule should be changed but the number of atoms in the skeleton and their connectivity, but not necessarily the bond orders, should remain the same.
Reaction of allyltrimethylsilane with a carbon electrophile to allylate the carbon electrophile.
Rearrangement of the acyl group in a phenolate ester to the ortho- and/or para-position. It is catalysed by a Lewis acid.
Can be promoted by heat or UV. The UV version (photo-Fries) involves a radical mechanism.
Rearrangement of the acyl group in a phenolate ester to the ortho-position.
Rearrangement of the acyl group in a phenolate ester to the para-position.
Formylation of a phenol or aromatic amine with hexamethylenetetramine in acidic conditions.
A molecular skeleton joining adjective that is satisfied by a chain part of a molecular skeleton being lengthened.
A molecular skeleton transformation objective that is satisfied by a reaction where the product has fewer rings than the reactants.
A molecular skeleton transformation objective that is satisfied by a reaction where an existing ring is reduced in size.
A carbon-carbon coupling reaction in which an aldehyde reacts with allyltrimethylsilane to form a homoallylic alcohol.
A carbon-carbon coupling reaction in which a ketone reacts with allyltrimethylsilane to form a homoallylic alcohol.
A molecular skeleton transformation objective that is satisfied by a reaction in which a functional group undergoes a change that does not affect the number of atoms in (or connectivity of) the skeleton of the molecule.
A molecular skeleton transformation objective that is satisfied by a reaction in which a single skeletal atom is removed from the end of a chain.
A functional group modification objective that is satisfied by a reaction in which a functional group is reduced.
A functional modification objective that is satisfied by a reaction in which two or more groups of atoms are added to the molecule, resulting in a change of skeletal bond order.
A molecular transformation objective that is satisfied by a reaction in which an existing skeletal ring is increased in size.
A molecular transformation objective that is satisfied by a reaction in which the number of skeletal rings in a molecule stays the same but the connectivity of the atoms in at least one ring changes.
A carbon-carbon coupling reaction between a beta-ketoester and an alkyl halide to yield an alpha-alkylated ester.
Subsequent treatment with mild hydrolysis leads to a ketone; concentrated base produces a substituted ester.
A reductive coupling reaction between two ester groups in the same molecule to give an acyloin (an alpha-hydroxyketone).
A reductive coupling reaction between two ester groups in different molecules to give an acyloin (an alpha-hydroxyketone).
A molecular transformation objective that is satisfied by a cleaving reaction in which a skeletal atom or group of atoms is removed from the middle of a molecule.
A molecular transformation objective that is satisfied by a reaction in which the parent molecule breaks up into three or more products.
A [2+2+1] cycloaddition between an alkyne, an alkene and carbon monoxide to form an alpha-beta-unsaturated cyclopentenone.
A molecular transformation objective that is satisfied by a reaction in which a fused ring system is present in a product that was not present in any of the reactants.
A molecular transformation objective that is satisfied by a reaction in which a large number of monomers react together to product a polymer consisting of repeating units.
A fused-ring-system formation reaction where a flavonol is produced by oxidation of a chalcone with alkaline hydrogen peroxide.
A molecular transformation objective that is satisfied by a reaction in which one singly-bonded substituent, but not a hydrogen, is replaced by another singly-bonded substituent.
Reaction of ortho-hydroxyaryl ketones with aromatic carboxylic acid anhydrides to yield a flavone.
Reaction of ortho-hydroxyaryl ketones with aromatic carboxylic acid anhydrides to yield an isoflavone.
Rearrangement of an aldose N-glycoside to a ketose N-glycoside by acid or base catalysis.
Reaction of a ketone with ethoxyacetylene to form an alkoxyethynyl alcohol.
Ring expansion of a 2-bromo-2-(alpha-bromobenzyl)-1-benzofuran to a flavonol in alcoholic alkali.
Reaction of ortho-hydroxyaryl ketones with aromatic acid anhydrides to yield a flavone or isoflavone.
Rearrangement of a propargyl alcohol to an alpha,beta-unsaturated carbonyl compound via an allene intermediate to yield the gamma-substituted product.
Rearrangement of a propargyl alcohol to an alpha,beta-unsaturated carbonyl compound via an enyne intermediate to yield the beta-substituted product.
A Horner-Wadsworth-Emmons reaction that uses phosphonates with electron-withdrawing groups and dissociating conditions to produce predominantly Z-olefins.
A molecular skeleton joining reaction where the connection formed is a carbon-carbon double bond.
Reaction of an aldehyde or ketone or carboxylic ester or amide with the Tebbe reagent to yield an olefin or an enol ether or an enamine.
Cyclization of a enynyl allene to yield a toluene biradical with radical centres on the methyl group and at the meta position.
Cyclization of a enynyl allene to yield a 1-methyl-5-methylenecyclopenta-1,3-diene biradical with radical centres on the methyl group and methylene group.
Copper-catalysed reaction of benzene with a nitrosylating agent and hydrogen peroxide to form an o-nitrosophenol.
A functional modification objective that is satisfied by deprotecting some functional group.
A functional modification objective that is satisfied by protecting some functional group.
A functional modification objective that is satisfied by a reaction in which two or more groups of atoms are removed from the molecule, resulting in a change of skeletal bond order.
molecular skeleton elimination objective
A molecular skeleton joining objective that is satisfied by a reaction in which one or more atoms are added to the middle of a chain.
A molecular skeleton joining objective that is satisfied by a reaction in which one or more atoms are added to the molecular skeleton and a skeletal rearrangement occurs.
A functional modification objective that is satisfied by a reaction in which a covalent bond is formed between the molecular skeleton and a functional group and where the skeletal bond order is unchanged.
A functional group modification objective that is satisfied by a reaction in which a functional group is oxidised.
Cyclisation of a propargyl alpha,beta-unsaturated ketone where the reactant rearranges to an allenyl vinyl ketone, followed by a Nazarov cyclisation in which a nucleophile 'intercepts' the intermediate carbocation to yield a cyclopentenone substituted at the alpha position opposite the double bond.
Rearrangement of an N-phenylhydroxamine in acid to yield a para-aminophenol.
Reaction of an aromatic diazonium compound with an alkali arsenite in the presence of copper or silver to yield an aromatic arsonic acid.
Reaction of an ortho-substituted nitroarene with a vinyl Grignard reagent to yield a 7-substituted indole.
Reaction of an aldehyde or ketone with a thioaldehyde or thioketone via a 1,3,4-thiadiazoline intermediate to yield an olefin.
Reaction of a nitroalkene with an alpha-isocyanoacetate to yield a substituted pyrrole.
A reaction in which the intended product is a pyrrole that was not present in any of the reactants.
Reduction of an aromatic nitro compound to the corresponding arene by iron in some form in aqueous acid.
Reaction of a benzofurazan 1-oxide with an enamine or enolate to yield a quinoxaline-1,4-dioxide.
Reaction of a beta-aminovinylketone with a Grignard reagent to yield a substituted alpha,beta-unsaturated carbonyl compound.
Reaction of an alpha-haloketone or alpha-haloether with a 1,3-dicarbonyl compound in the presence of pyridine to yield a substituted furan.
Rearrangement of a mancude eight-membered system containing a pentacycle into a different pentacycle where two of the ring atoms are ring atoms in the original molecule.
Rearrangement of an azapentacycle containing a -N= system where there is an unsaturated three-heavy-atom substituent XYZ on the substituent double-bonded to the nitrogen, to a new azapentacycle where the pivotal nitrogen has broken its single bond and formed a new bond with atom Z.
monocyclic Boulton-Katritzky rearrangement
Rearrangement of a mancude bicyclo[4.3.0] compound with an unsaturated two-heavy-atom substituent on the six-membered ring alpha to the bridgehead to form a new mancude bicyclo[4.3.0] compound where the five-membered ring has been formed from the two-heavy-atom substituent and the original five-membered ring has been broken.
bicyclic Boulton-Katritzky rearrangement
Reaction of a primary nitro compound with phenyl isocynatate and triethylamine to yield a nitrile oxide.
Reaction of an aldehyde or ketone with a sodium acetylide to yield a propargyl alcohol.
Reaction of an ester with an electron-withdrawing group alpha- to the ester functionality with a metal halide or pseudohalide to yield the shorter homologous system.
Reaction of an aromatic nitro compound with an unsaturated substituent at the alpha-position to form a fused-ring nitrogen heterocycle.
A Cadogan cyclization that results in an indole.
Addition of hydrogen atoms to unsaturated rings by means of alkali metals in low-molecular weight amines.
Reaction of an N-(2-alkylphenyl)alkanamide with strong base to form an indole.
Reaction of a N-(2-alkylphenyl)-trimethylsilylamine with two equivalents of organolithium and an ester or carboxylic acid to form an indole.
Rearrangement of an acyl imidate to form a carboximide.
Rearrangement of an aryl imino ether to yield an N,N-diaryl amide.
Reaction of an acetylated amino acid with an aldehyde then with a second amino acid, then hydrogenation and hydrolysis to form a dipeptide. It proceeds via an azlactone intermediate.
Removal of a terminal amino acid residue from a peptide by benzoylation, azidation, treatment with benzyl alcohol, hydrogenation and hydrolysis.
Removal of a terminal amino acid residue from a peptide.
terminal amino-acid residue cleaving reaction
Ring formation reaction where the intended product is an acridine.
Reaction of a diarylamine in an organic acid or anhydride in the presence of zinc chloride to yield a 9-substituted acridine.
Definition source Merck Index, modified for errors.
Ring formation reaction where the intended product is a pyridine.
Ring formation reaction where the intended product is a carbazole.
Reaction of a phenol, an aromatic aldehyde and a primary aromatic or heterocyclic amine to yield a Betti's base, also known as an alpha-aminobenzylphenol.
Reaction of a terminal hydroxyketone or terminal halogenoketone with an aromatic amine to yield a 2-substituted indole.
Originally this involved a solvent but this need not be the case, see for example doi:10.1039/b719641e
Cyclisation of an o-acylaminoacetophenone in alcoholic sodium hydroxide to form a substituted hydroxyquinoline.
The substituent on the amino nitrogen can affect the ratio of 1-hydroxy to 3-hydroxy products.
Palladium-catalysed coupling of copper(I) acetylides with aryl halides to yield arylacetylenes.
Reaction of carbonyl compounds with ammonia or an amine to yield a pyridine.
Reaction of an azacycle with an alkali-metal amide to yield an aminated azacycle.
Reaction of a carboxylic ester with a magnesium iodide alkylamide to yield a carboxamide.
Condensation of beta-phenylethylmagnesium bromide with a cyclohexanone followed by cyclisation and dehydration in concentrated sulfuric acid to yield an octahydrophenanthrene.
Reaction of a hydroxylated anthraquinone with fuming sulfuric acid or sulfuric acid in boric acid in the presence of a mercury or selenium catalyst to form a more hydroxylated anthraquinone.
Etherification of an aldehyde followed by bromination and reaction with a Grignard reagent followed by treatment with zinc to eliminate the halogen and alkoxy groups to produce an olefin.
Rearrangement of a cyclohexanone phenylhydrazone followed by oxidation to yield a carbazole.
Reaction of an organomagnesium or organolithium compound with an N,N'-disubstituted formamide to yield the next homologous aldehyde.
Diels-Alder reaction of a dienophile with a cationic aromatic azadiene to yield a bridged-ring system.
Reaction of an ortho-acyldiarylmethane, catalysed by acid, to yield an anthracene.
Reaction of a bromoarene that has an electrophilic group at the para-position with lithium bromide or lithium iodide followed by intramolecular cyclisation to yield a fused-ring system.
Reaction of an aliphatic aldehyde with a phenolic ether and hydrochloric acid to yield an alpha-chloroalkylphenolic ether.
Elimination of a water molecule from a secondary alcohol to yield an olefin.
Elimination of a hydroxylamine from an amine oxide by pyrolysis to yield an olefin.
Reaction of an aniline with a nitrile in the presence of boron trichloride and a Lewis acid to yield an ortho-acylated aniline.
A cross-coupling reaction between a Grignard reagent and an activated (aryl or vinyl) halide or triflate. The reaction is catalysed by a palladium catalyst.
A cross-coupling reaction between a Grignard reagent and an activated (aryl or vinyl) halide or triflate. The reaction is catalysed by a nickel catalyst.
Reaction of a 1,2-diol with triethoxymethane under heat to yield an olefin.
The reaction is stereospecific. It proceeds via a 1,3-dioxolane intermediate.
Reaction of silyl enol ethers with palladium acetate in acetonitrile to yield an alpha,beta-unsaturated ketone.
Reaction of diphenylthiourea with lead carbonate and potassium cyanide to form a cyanoformidine followed by ring closure and acid hydrolysis to yield isatin.
Reaction of aniline, hydroxylamine and chloral hydrate to form an aniline intermediate followed by cyclization in acid and hydrolysis to yield isatin.
Sandmeyer isonitrosoacetanilide isatin synthesis
Oxidation of an alcohol with a pyridine-chromium trioxide complex to yield a carbonyl compound.
Oxidation of a primary alcohol with a pyridine-chromium trioxide complex to yield an aldehyde.
Oxidation of a secondary alcohol with a pyridine-chromium trioxide complex to yield a ketone.
Oxidation of a primary alcohol with a pyridine-chromium trioxide complex in dichloromethane to yield an aldehyde.
A functional group modification where a carbonyl oxygen is replaced by an imine.
Reductive amination of an aldehyde with ammonium formate or formamide to form an amine.
Reductive amination of a ketone with ammonium formate or formamide to form an amine.
Conversion of an alcohol to an alkyl bromide with triphenylphosphine and tetrabromomethane.
Appel bromination with tetrabromomethane
Conversion of an alcohol to an alkyl bromide with triphenylphosphine and bromine.
Reaction of an aldehyde with tetrabromomethane and triphenylphosphine to yield a terminal dibromoolefin.
This is the first step of the Corey-Fuchs reaction. The second step is the Fritsch-Buttenberg-Wiechell rearrangement.
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000624 for Heck-type reaction and RXNO:0000603 for cross-coupling.
obsolete: Heck-type reaction/cross-coupling
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000625 for the bromo Heck reaction and RXNO:0000604 for Liebeskind-Srogl coupling.
obsolete: bromo Heck reaction/Liebeskind-Srogl coupling
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000626 for the chloro Heck reaction and RXNO:0000605 for Fukuyama coupling.
obsolete: chloro Heck reaction/Fukuyama coupling
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000627 for the iodo Heck reaction and RXNO:0000606 for the chloride Finkelstein reaction.
obsolete: iodo Heck reaction/chloride Finkelstein reaction
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000628 for the triflyloxy Heck reaction and RXNO:0000607 for the bromide Finkelstein reaction.
obsolete: triflyloxy Heck reaction/bromide Finkelstein reaction
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000629 for the bromo Heck-type reaction and RXNO:0000608 for the sulfonate ester Finkelstein reaction.
obsolete: bromo Heck-type reaction/sulfonate ester Finkelstein reaction
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000630 for the chloro Heck-type reaction and RXNO:0000609 for Sandmeyer fluorination.
obsolete: chloro Heck-type reaction/Sandmeyer fluorination
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000631 for acyclic Beckmann rearrangement and RXNO:0000610 for Sandmeyer chlorination.
obsolete: acyclic Beckmann rearrangement/Sandmeyer chlorination
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000632 for Baeyer-Emmerling indole synthesis and RXNO:0000611 for Sandmeyer bromination.
obsolete: Baeyer–Emmerling indole synthesis/Sandmeyer bromination
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000633 for bromo Sonogashira coupling and RXNO:0000612 for Sandmeyer iodination.
obsolete: bromo Sonogashira coupling/Sandmeyer iodination
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000634 for bromo Suzuki coupling and RXNO:0000613 for the iodo Heck reaction.
obsolete: bromo Suzuki coupling/iodo Heck reaction
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000635 for bromo Suzuki-type coupling and RXNO:0000628 for the triflyloxy Heck reaction.
obsolete: bromo Suzuki-type coupling/triflyloxy Heck reaction
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000636 for bromolactonization and RXNO:0000629 for the bromo Heck-type reaction.
obsolete: bromolactonization/bromo Heck-type reaction
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000637 for chloro Sonogashira coupling and RXNO:0000630 for the chloro Heck-type reaction.
obsolete: chloro Sonogashira coupling/chloro Heck-type reaction
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000638 for chloro Suzuki coupling and RXNO:0000624 for the Heck-type reaction.
obsolete: chloro Suzuki coupling/Heck-type reaction
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000639 for chloro Suzuki-type coupling and RXNO:0000625 for the bromo Heck reaction.
obsolete: chloro Suzuki-type coupling/bromo Heck reaction
This term has been obsoleted because the ID was inadvertently reused for two classes. See RXNO:0000640 for chlorolactonization and RXNO:0000626 for the chloro Heck reaction.
obsolete: chlorolactonization/chloro Heck reaction
A Beckmann rearrangement which produces a cyclic product.
A Dess-Martin oxidation of a primary alcohol to an aldehyde.
A Dess-Martin oxidation of a secondary alcohol to a ketone.
Synthesis of a quinoline by reaction of a 2-aminobenzaldehyde with a ketone.
Reaction of an aldehyde or ketone with an alpha-cyanoester to form a 2-aminothiophene.
A Sonogashira coupling where the aryl halide is an aryl iodide.
A Suzuki coupling where the halide is an iodide.
A Suzuki-type coupling where the halide is an iodide.
A halolactionization where the halide is an iodide.
An azacycle synthesis where the product is a 4-oxo-3,4-dihydroquinazoline and the reactants are a 2-aminobenzoic acid and an amide.
A quinoline synthesis where the product is a gamma-hydroxyquinoline and the reactants are a 2-aminobenzoic acid and an aldehyde or ketone.
An azacycle synthesis where the product is an isoquinoline and the reactants are a benzaldehyde and a 2,2-dialkoxyethylamine.
An O-acylation to ester where dicyclohexylcarbodiimide is used as a coupling reagent and 4-dimethylaminopyridine as a catalyst.
A Sonogashira coupling where the role of the halide is played by a triflyloxy group.
A Suzuki coupling where the rule of the halide is played by a triflyloxy group.
A Suzuki-type coupling where the rule of the halide is played by a triflyloxy group.
Synthesis of an aziridine by dehydrating a beta aminoalcohol with sulfuric acid.
Reaction of an alpha-diketone with a dialkyl thiodiacetate to form a thiophene dicarboxylic acid.
The coupling of a boronic acid or boronic ester with an unsaturated halide, triflate or sulfonate.
Addition of a carboxylic acid oxygen and halogen across a carbon-carbon double bond to form a lactone.
Expansion of a pyrrole ring by heating with a halogeno compond to form a 3-halogenopyridine.
Condensation of an aromatic aldehyde with an aliphatic aldehyde or ketone in the presence of a relatively strong base to from an alpha,beta-unsaturated aldehyde or ketone.
this ID has been obsoleted because it was used for two different classes.
obsolete: Combes quinoline synthesis/Conrad%E2%80%93Limpach_synthesis
Enantioselective reduction of a ketone to an alcohol with a chiral oxazaborolidine.
Reaction of a sulfur ylide with a double-bond to produce a three-membered ring.
Reaction of a sulfur ylide with a ketone to produce an epoxide.
Johnson-Corey-Chaykovsky epoxide synthesis
Reaction of a sulfur ylide with an olefin to produce a cyclopropane.
Johnson-Corey-Chaykovsky cyclopropane synthesis
Reaction of a sulfur ylide with an imine to produce an aziridine.
Johnson-Corey-Chaykovsky aziridine synthesis
Reaction of a sulfur ylide with a thione to produce a thiirane.
Johnson-Corey-Chaykovsky thiirane synthesis
A joining reaction where a carbon-carbon bond is formed between unlike moieties.
A cross-coupling reaction where a thioester and a boronic acid react to form a ketone. It uses a metal catalyst.
A cross-coupling reaction where a thioester and an organozinc halide react to form a ketone. It uses a palladium catalyst.
The conversion of an alkyl chloride to an alkyl iodide by SN2 substitution.The reaction relies upon the equilibrium being pushed to completion by precipitation.
The conversion of an alkyl bromide to an alkyl iodide by SN2 substitution.The reaction relies upon the equilibrium being pushed to completion by precipitation.
The conversion of an alkyl sulfonate ester to an alkyl iodide by SN2 substitution.The reaction relies upon the equilibrium being pushed to completion by precipitation.
An aromatic substitution reaction where an aryl diazonium salt reacts with a copper(I) fluoride to form an aromatic fluoride.
An aromatic substitution reaction where an aryl diazonium salt reacts with a copper(I) chloride to form an aromatic chloride.
An aromatic substitution reaction where an aryl diazonium salt reacts with a copper(I) bromide to form an aromatic bromide.
An aromatic substitution reaction where an aryl diazonium salt reacts with a copper(I) iodide to form an aromatic iodide.
A planned reaction in which one of the products contains an imidazole system that was not in any of the reactants.
A planned reaction in which one of the products contains an indazole system that was not in any of the reactants.
A planned reaction in which one of the products contains a piperazine system that was not in any of the reactants.
A planned reaction in which one of the products contains a piperidine system that was not in any of the reactants.
A planned reaction in which one of the products contains a pyrrolidine system that was not in any of the reactants.
An azacycle synthesis in which pyrrolidines or piperidines are formed by decomposition of protonated N-haloamines.
A Hofmann-Löffler-Freytag reaction in which the product is a piperidine.
Hofmann-Löffler-Freytag piperidine synthesis
A Hofmann-Löffler-Freytag reaction in which the product is a pyrrolidine.
Hofmann-Löffler-Freytag pyrrolidine synthesis
An alpha-halogenation reaction where a carboxylic acid reacts with dibromine to form an alpha-bromocarboxylic acid.
Meerwein-Ponndorf-Verley reduction of an aldehyde to the corresponding primary alcohol.
Meerwein-Ponndorf-Verley reduction of an aldehyde
Meerwein-Ponndorf-Verley reduction of a ketone to the corresponding secondary alcohol.
Meerwein-Ponndorf-Verley reduction of a ketone
A carbon-carbon coupling reaction where an organohalide or triflate couples to a terminal olefin to produce an internal olefin.
A Heck reaction where an organobromide couples to a terminal olefin to produce an internal olefin, catalysed by palladium.
A Heck reaction where an organochloride couples to a terminal olefin to produce an internal olefin, catalysed by palladium.
A Heck reaction where an organoiodide couples to a terminal olefin to produce an internal olefin, catalysed by palladium.
A Heck reaction where an organotriflate couples to a terminal olefin to produce an internal olefin, catalysed by palladium.
A Heck-type reaction where an organobromide couples to a terminal olefin to produce an internal olefin.
A Heck-type reaction where an organochloride couples to a terminal olefin to produce an internal olefin.
A Beckmann rearrangement where an acyclic amide is formed.
An indole synthesis where an ortho-nitrocinnamic acid reacts with iron powder in a basic solution to form an indole.
A Sonogashira coupling where the aryl halide is an aryl bromide.
A Suzuki coupling where the halide is a bromide.
A Suzuki-type coupling where the halide is a bromide.
A halolactionization where the halide is a bromide.
A Sonogashira coupling where the aryl halide is an aryl chloride.
A Suzuki coupling where the halide is a chloride.
A Suzuki-type coupling where the halide is a chloride.
A halolactionization where the halide is a chloride.
Reaction of an arylamine wtih a beta-ketoester to yield a 4-hydroxyquinoline.
Reaction of a beta-diketone with a primary arylamine to yield a quinoline. It is acid-catalysed.
A 1,3-dipolar cycloaddition reaction where a fullerene reacts with an aldehyde and an amino acid to form a pyrrolidinofullerene.
A rearrangement of a 2-furylcarbinol to a 4-hydroxycyclopentenone. It is acid-catalysed.
A ring-breaking reaction where a pyrrolidinofullerene yields a fullerene. The substituted fullerene is heated with a dipolarophile and a catalyst.
A cycloaddition where a fullerene reacts with diethyl bromomalonate to form a methanofullerene.
A cyclisation where a hydroxyl group acts as the nucleophile in a Wacker-Tsuji oxidation accompanied by beta-hydride elimination, forming a ring.
A cyclisation where an amino group acts as the nucleophile in a Wacker-Tsuji oxidation accompanied by beta-hydride elimination, forming a ring.
A cleaving reaction where an olefin is dihydroxylated with osmium tetroxide and undergoes a Malaprade reaction to yield two aldehydes, two ketones, or an aldehyde and a ketone.
A cleaving reaction of a 1,2-diol using periodic acid to give the corresponding carbonyl compounds.
The oxidation of a 1,2-glycol with Fenton's reagent (hydrogen peroxide and iron salts) to give an alpha-hydroxy aldehyde.
The oxidation of an alpha-hydroxy carboxylic acid with Fenton's reagent to give an alpha-keto carboxylic acid.
Fenton alpha-hydroxy carboxylic acid oxidation
The reaction of the components of Fenton's reagent, viz. reduction of hydrogen peroxide by Fe(II) , producing an hydroxyl radical.
The Mukaiyama hydration is an organic reaction involving formal addition of an equivalent of water across an alkene by the action of catalytic bis(acetylacetonato)cobalt(II) complex, phenylsilane and atmospheric oxygen.
Mukaiyama hydration
A reaction between an alkyne and a carbonyl group under basic conditions in which a terminal alkyne serves as the CH-acidic moiety. When the carbonyl is an aldehyde, the 'Favorskii rearrangement' (RXNO:0000385) takes place and leads to an enone.
Favorskii reaction
Reductions with diimide are a chemical reactions that convert unsaturated organic compounds to reduced alkane products. In the process, diimide is oxidized to dinitrogen.
Diimide reduction
A protection reaction where the reactive centre is a carbonyl oxygen.
carbonyl group protection
The acid-catalyzed formation of an acetal (or ketal) to protect a carbonyl group by nucleophilic addition of an alcohol to an aldehyde (or ketone) with the elimination of water.
acetal protection
A chemical reaction that allows the generation of boronates from vinyl or aryl halides with the cross-coupling of bis(pinacolato)diboron under basic conditions.
Miyaura borylation
A chemical reaction for the stereoselective synthesis of an olefin from a 1,2-diol.
Corey-Winter elimination
The Tsuji-Wilkinson decarbonylation reaction is a method for the decarbonylation of aldehydes and some acyl chlorides.
Tsuji-Wilkinson decarbonylation
Although decarbonylation can be effected by several transition metal complexes, Wilkinson's catalyst has proven the most effective.
A chemical reaction in which ketones are synthesized from formaldehyde or other aldehydes, involving a temporary repolarization of a carbonyl group.
Corey-Seebach reaction
Usually, the aldehyde is first reacted with propane-1,3-dithiol to form a 1,3-dithiane, which then reacts with an electrophile after deprotonation with n-butyllithium.
Nitroxide exchange reactions are based on thermal C–O bond homolysis of alkoxyamines, which leads to transient carbon-centred radicals and persistent nitroxide radicals. Usually these carbon centred radicals are quickly trapped by the nitroxide radicals and reform the alkoxyamines.
IUPAC does not recommend the use of the often synonymously used terms "nitroxyl radicals" or "nitroxides" for the class of "aminoxyl radicals".
nitroxide exchange reaction
The conversion of pyran or pyrone (pyranone) derivatives to the corresponding pyridine derivative.
Baeyer pyridine synthesis
Oxidation of primary and secondary alcohols via their alkoxysulfonium salts. Upon the addition of base, the salt rearranges intramolecularly to aldehydes and ketones, respectively.
Corey-Kim oxidation
Oxidation of primary and secondary alcohols to aldehydes and ketones, respectively, through the use of pyridinium chlorochromate (PCC).
Corey-Suggs oxidation
Oxidation of primary and secondary alcohols to aldehydes and ketones, respectively, through the use of pyridinium dichromate (PDC).
Corey-Schmidt oxidation
A particularly mild oxidation method in which, for example, dimethyl sulfoxide and acetic anhydride can be used as oxidizing agents to selectively produce aldehydes from primary alcohols without further oxidation to carboxylic acids. Analogously, secondary alcohols can be oxidized to form ketones.
Albright-Goldman oxidation
The Rubottom oxidation is a useful, high-yielding chemical reaction between silyl enol ethers and peroxy acids to give the corresponding α-hydroxy carbonyl product.
Rubottom oxidation
A three-component reaction (3CR) of a heterocyclic amidine, an aldehyde, and an isocyanide, resulting in a cyclic compound with imidazo[1,2-a] heterocycle as the core structure.
Groebke-Blackburn-Bienaymé reaction
The preparation of oxindole/indolin-2-one from 2-nitrophenylacetic acid by reduction of the nitro group and subsequent dehydration.
Baeyer oxindole synthesis
Condensation of a formamide acetal with a derivative of o-nitrotoluene to yield an enamine intermediate that subsequently undergoes reductive cyclization to give the corresponding indole.
Leimgruber-Batcho indole synthesis
Oxidation of alcohols to the corresponding carbonyl product using 2-iodoxybenzoic acid (IBX) as oxidizing agent.
IBX oxidation and Dess-Martin oxidation are alcohol oxidation by hypervalent iodine reagents. The Dess-Martin periodinane used for oxidation in the Dess-Martin oxidation is prepared by reacting IBX with acetic anhydride in DMSO.
IBX oxidation
A chemical reaction in which a carboxylic acid (or its salt) reacts with an organic (alkyl or aryl) halide to form a new carbon-carbon bond with concomitant loss of CO2. In addition, the reaction requires a metal catalyst, a base and an oxidizing agent.
decarboxylative cross-coupling
A carbon-carbon coupling reaction between an arene and an alkene to give a substituted arene. The reaction is catalysed by a Lewis acid.
Balsohn alkylation
A three-component condensation reaction in which primary or secondary amines react with a carbonyl compound (aldehyde or ketone) and a dialkyl phosphonate (also called dialkyl phosphite) to form an alpha-aminophosphonate.
Kabachnik-Fields reaction
A polymerisation reaction in which phenol and formaldehyde react together in a chain reaction to form a phenol formaldehyde resin (also infrequently called phenoplast).
Baekeland-Manasse-Lederer reaction
The rearrangement of an alpha-haloketone into an ester with a tertiary alpha-carbon atom by intramolecular migration of an alkyl or aryl group.
Aston-Greenburg rearrangement
The rearrangement/migration of alkyl groups in polyalkylbenzenes or polynuclear aromatic compounds in the presence of anhydrous aluminum chloride or the mixture of protonic acid and Lewis acid.
Baddeley isomerization
The reduction of a thioester to an aldehyde by a silyl hydride in the presence of catalytic amounts of palladium.
Fukuyama reduction
A three component cyclization of an aromatic or vinylic alkoxy pentacarbonyl chromium carbene complex, an alkyne and carbon monoxide to give a Cr(CO)3 coordinated phenol.
benzannulation reaction of Fischer carbene complexes
Dötz reaction
The formation of a substituted cyclopropanol by reaction of a carboxylic ester with a Grignard reagent (carrying a hydrogen atom in the beta-position) in the presence of a titanium(IV) alkoxide as catalyst. A modified cyclopropanol product can be generated by addition of a terminal alkene as a further reactant.
The dialkyldialkoxytitanium reagent, which actually reacts with the carboxylic ester, is generated in situ from the Grignard reagent and the titanium(IV) alkoxide.
Kulinkovich reaction
The formation of a substituted cyclopropylamine by reaction of an amide with a Grignard reagent (carrying a hydrogen atom in the beta-position) in the presence of a titanium(IV) alkoxide as catalyst.
The Kulinkovich-de Meijere reaction is a modification of the Kulinkovich reaction (i.e., the reaction of an amide instead of a carboxylic ester under Kulinkovich conditions).
Kulinkovich-de Meijere reaction
The formation of a substituted primary cyclopropylamine by reaction of a nitrile with a Grignard reagent (carrying a hydrogen atom in the beta-position) in the presence of a titanium(IV) alkoxide as catalyst.
The Kulinkovich-Szymoniak reaction is a modification of the Kulinkovich reaction (i.e., the reaction of a nitrile instead of a carboxylic ester under Kulinkovich conditions).
Kulinkovich-Szymoniak reaction
Chiral (salen)manganese(III)-catalyzed asymmetric epoxidation of alkenes. In addition to the catalyst, stoichiometric amounts of an oxidant (e.g. sodium hypochlorite) are required.
Jacobsen epoxidation
Organocatalytic enantioselective epoxidation of trans- and tri-substituted olefins using a fructose derived chiral ketone catalyst and potassium peroxomonosulfate or H2O2 as an oxidant.
Shi epoxidation
A multicomponent reaction (A-4CR) in which 3-thiazolines (2,5-dihydro-1,3-thiazoles) or mixtures of several 3-thiazolines are synthesized from elemental sulfur, an alpha-substitutable ketone or aldehyde, another carbonyl component and ammonia.
Asinger reaction
Cleavage of methyl ketones (i.e. oxidative demethylation) with halogens (or hypohalites) in the presence of a base to give a carboxylic acid and haloform (trihalomethane).
haloform reaction
The conversion of dialkyl phosphites (dialkyl phosphonates) to dialkyl chlorophosphates using tetrachloromethane and a base (usually a primary, secondary or tertiary amine).
Since the dialkyl chlorophosphates formed are often too reactive to be isolated, conversion to the corresponding phosphate or phosphoramidate occurs in the presence of a suitable nucleophile (e.g., alcohol or amine) after the actual Atherton-Todd reaction.
Atherton-Todd reaction
Synthesis of diarylmethane derivatives using an aldehyde and an aromatic compound at low temperature in an acidic medium.
A Friedel-Crafts type reaction proceeding via electrophilic aromatic substitution.
Baeyer diarylmethane synthesis
A hydroxyl group deprotection in which an silyl ether group is transformed into a hydroxy group.
silyl deprotection