Table of Contents

ALKYLATION AND RELATED REACTIONSREACTIONS OF ALLYL AND BENZYL RELATED CARBANIONS WITH ALKYL AND ACYL ELECTROPHILESAlkylation of allyl and benzyl derivativesAlkylation of allyl, benzyl and related aminesVia aminooxazolinesVia formamidinesOther derivativesAllyl related systemsBenzyl related systemsReaction of allyl ether equivalentsa-Alkylationa-AcylationOther electrophilesAlkylation of vinyl ethersa-Alkylation of allyl and benzyl related silanesAllenic ether tandem acylation-cyclizationREACTIONS OF ALDEHYDE DERIVATIVES WITH ALKYL AND OTHER ELECTROPHILESSimple aldehydesa-AlkylationVia hydrazone derivativesVia imine and enamine derivativesa-Hydroxylationa-SilylationSequential silylation + alkylationa-Phosphinylationa-Thiolationa-Heterosubstituted aldehydesa-Alkylationa-Amino derivativesa-Oxy derivativesSequential alkylation + nucleophilic additiona-Silyl derivatives - sequential reactionsAlkylation + alkylationAlkylation + acylationa-Phosphino derivativesa-Thio derivativesSequential alkylation + acylationREACTION OF KETONE DERIVATIVES WITH ALKYL AND OTHER ELECTROPHILESa-AlkylationAcyclic systems with auxiliary on the ketoneSimple ketone derivativesb-Dicarbonyl derivativesb-Keto ester derivativesCyclic systems with auxiliary on the ketoneSimple ketone derivativesCyclopentanone derivativesCyclohexanone derivativesHigher order cyclic ketonesb-Dicarbonyl derivativesb-Keto ester and equivalent derivativesa-Heteroatom substituted ketone derivativesa-Dicarbonyl and related derivativesa-Nitronate substituted derivativesa-Thio substituted derivativesa,a¢-Diamino substituted derivativesa,a¢-Dioxy substituted derivativesReaction with other electrophilesa-Acylationa-Aminationa-Hydroxylationa-SilylationSequential silylation + alkylationa-Phosphinylationa-HalogenationREACTION OF CARBOXYLIC ACID DERIVATIVES WITH ALKYL AND OTHER ELECTROPHILESa-AlkylationC2-Acid derivatives (acetate equivalents)Creation of an a-stereocentre (sequential bisalkylation)Creation of a b-stereocentre (kinetic resolution and related)Phenylacetic acid derivatives Unsubstituted phenyl ring derivativesAromatic ring-modified derivativesOther related derivativesC3-Acid derivatives (propionate equivalents)Reaction with C1-electrophilesMethyl derivativesBenzyl derivativesReaction with C2-electrophilesEthyl derivativesSubstituted ethyl derivativesReaction with C3-electrophilesPropyl and substituted propyl derivativesAllyl and related derivativesReaction with C4-electrophilesButyl derivativesSubstituted butyl derivativesReaction with C5-electrophilesReaction with higher order electrophilesReaction with sundry heterocyclic electrophilesPhenylpropionic acid derivativesUnsubstituted phenyl ring derivativesAromatic ring-modified derivativesMalonic acid and related derivativesBisalkylation of unsubstituted derivativesReaction of monosubstituted derivativesReaction of miscellaneous substituted C3-acid derivativesb-Oxo acid derivativesAcyclic systemsCyclic systemsC4-Acid derivativesUnsubstituted butanoic acid derivativesUnsaturated and carbon substituted derivativesSuccinic acid and related derivativesOther heteroatom substituted derivativesC5-Acid derivativesUnsubstituted pentanoic acid derivativesUnsaturated and carbon substituted derivativesHeteroatom substituted derivativesC6-Acid derivativesUnsubstituted hexanoic acid derivativesUnsaturated and carbon substituted derivativesHeteroatom substituted derivativesHigher order acid derivativesa-Amino acid derivativesAuxiliary on the acidGlycinate equivalentsAlanate equivalentsHigher order amino acid equivalentsAuxiliary on the nitrogenGlycinate equivalentsAlanate equivalentsHigher order amino acid equivalentsAuxiliary on both acid and nitrogenIndividual auxiliariesSingle auxiliary (bislactim ethers / cyclic Schiff bases / oxazinones)Glycinate equivalentsAlanate equivalentsHigher order amino acid equivalentsOther a-heteroatom substituted acid derivativesa-Oxy derivativesGlycolic acid derivativesHigher order derivativesa-Thio derivativesa-Halogeno derivativesa-Silyl derivativesLactonesLactamsMonofunctional systemsBicyclic lactams (g- and d-oxo acid derivatives)a-Acylation of acid derivativesa-Amination of acid derivativesElectrophilic amino equivalents with the auxiliary on the nucleophileElectrophilic amino equivalents with the auxiliary on the electrophileNucleophilic amino equivalents (halogenation + substitution)a-Amination of phosphonic acid derivativesa-Hydroxylation of acid derivativesa-Silylation of acid derivativesa-Thiolation of acid derivativesa-Selenation of acid derivativesa-Halogenation of acid derivativesREACTION OF PHOSPHORIC ACID DERIVATIVES WITH ALKYL AND OTHER ELECTROPHILESa-AlkylationAlkyl and aralkyl derivativesa-Chloro derivativesa-Amino derivativesAuxiliary on nitrogenAuxiliary on phosphorusa-Aminationa-HalogenationALKYLATION OF SULFONAMIDES WITH THE AUXILIARY ON NITROGENMISCELLANEOUS RELATED REACTIONSProtonation of auxiliary-bearing substratesDynamic kinetic resolution with auxiliary-bearing electrophilesCarbon nucleophilesNitrogen nucleophilesOxy-nucleophilesThio-nucleophilesHalo-nucleophilesWittig-type reactionsDeracemization via acylationSundry reactions of acid derivatives with auxiliary-bearing electrophilesFriedel-Crafts type reactionsReaction of arenechromium tricarbonyl carbanions with alkyl and hetero electrophilesAromatic substitutionNucleophilicRadicalREFERENCESADDITION TO C=C BONDSREDUCTION AND RELATED REACTIONSCatalytic hydrogenationCarbon substituted a,b-unsaturated acyl derivativesHeteroatom substituted a,b-unsaturated acyl derivativesa-Nitrogen substitutedb-Nitrogen substitutedb-Oxygen substitutedAromatic systemsDissolving metal reduction of aromatic systemsTandem reductive alkylation of acyl substituted aromatic systemsENE REACTIONSADDITION OF HALO-CONTAINING ADDENDSHalogenationHalohydrin formationHalolactonizationOtherDIHYDROXYLATIONMono- and disubstituted C=CTrisubstituted C=CEPOXIDATIONMonosubstituted C=CDisubstituted C=CTrisubstituted C=CCYCLOPROPANATIONAuxiliary on acceptorMono- and disubstituted acyclic alkenesTrisubstituted acyclic alkenesCycloalkenes with unsubstituted C=CCycloalkenes with substituted C=CAuxiliary on donorIntramolecularTandem cyclopropanation + rearrangementCYCLOPROPENATIONRADICAL ADDITIONAuxiliary on acceptor alkeneIntermolecularIntramolecularAuxiliary on donor radicalIntermolecularIntramolecularCONJUGATE AND RELATED ADDITION TO ELECTROPHILIC C=C BONDSAuxiliary on the donor nucleophile - simple additionAcyl anion equivalents Formyl derivativesHigher order derivativesAldehyde-derived enolate equivalentsKetone-derived enolate equivalentsAlkyl ketone derivativesAralkyl ketone derivativesCyclic ketone derivatives1,3-Dicarbonyl derivatives (b-keto esters and b-diketones)Intramolecular reactionsAcyl enolate equivalentsSimple acyl derivativesLactam and lactone derivativesIntramolecular reactionsa-Amino acid derivatives - auxiliary on nitrogen (glycinate and alaninates)a-Amino acid derivatives - auxiliary bonded to both acyl and nitrogen (bislactims and Ni complexes)a-Alkoxy acyl derivatives (glycolates)Conjugated phosphonamide anions (allyl/crotyl)Transition metal complexed aryl nucleophilesNitrogen heteronucleophilesAuxiliary on the donor nucleophile - tandem additionAcyl-anion equivalents - conjugate addition + alkylationCarbonyl-based donor nucleophilesConjugate addition + alkylationConjugate addition + acylationConjugate addition + aldol reactionOthersAcyl enolate equivalentsNitrogen heteronucleophiles - conjugate addition + alkylationAuxiliary on donor - radical additionAuxiliary on acceptor a,b-unsaturated system - simple additiona,b-Unsaturated aldehyde-based derivativesAddition of carbon nucleophilesAddition of heteronucleophilesa,b-Unsaturated ketone-based derivativesa,b-Unsaturated acyl derivatives - addition of carbon nucleophilesAcrylic / methacrylic and related derivativesCrotonic and tiglic acid derivativesAddition of aliphatic nucleophilesAddition of aromatic nucleophilesPhenyl organometallic reagentsSubstituted phenyl organometallic reagentsMalonic and b-keto ester derivativesHigher order aliphatic acyl derivativesUnfunctionalized acyl derivativesFunctionalized derivativesa,b-Unsaturated aromatic acyl derivativesCinnamic acid and related derivativesReaction of organometallic reagentsReaction of enolate derivativesSubstituted aromatic and heteroaromatic derivativesb-Heteroatom substituted derivativesa,b-Unsaturated acyl derivatives - addition of heteronucleophilesHydride (conjugate reduction)Nitrogen derivativesAlkoxidesThiolatesSilyl anionsHalidesOther activated systemsa,b-Unsaturated sulfoximine and sulfonic acid derivativesa,b-Unsaturated nitro derivatives (addition/elimination)Activated aromatic acid derivatives1,4-Addition to pyridinium systemsN-alkyl derivativesN-acyl derivativesIntramolecular reactionsAuxiliary on acceptor a,b-unsaturated system - tandem addition of carbon nucleophilesCarbonyl-based derivatives - conjugate addition + alkylationAcyl-based derivativesConjugate addition + alkylationConjugate addition + acylation/amination/hydroxylation/thiolation/ halogenationConjugate addition + conjugate additionConjugate addition + C=N additionConjugate addition + aldol reactionConjugate addition + miscellaneousAuxiliary on acceptor a,b-unsaturated system - tandem addition of heteronucleophilesConjugate addition + alkylationHydride (reductive alkylation)Nitrogen derivativesTin derivativesConjugate addition + others (conjugate addition / acylation / aldol / halogenation)Auxiliary on acceptor a,b-unsaturated system - radical additionNucleophilic addition to transition-metal alkene/arene complexesAuxiliary on the donor nucleophileAuxiliary on the acceptor transition-metal complexREFERENCESADDITION REACTIONS TO C=N BONDSREDUCTION OF IMINES, IMINIUM IONS, HYDRAZONES AND OXIMESENE REACTIONSNUCLEOPHILIC ADDITIONImines and oximes - auxiliary on nitrogenCarbon-based nucleophilesPhosphite nucleophilesImines and oximes - auxiliary on carbonGlyoxal and glycolate derivativesPyruvaldehyde derivativesOthersImines - auxiliary on nucleophileAddition of simple enolate equivalentsAcetate and related derivativesPropionate and related derivativesHigher order derivativesAddition of a-heteroatom substituted enolatesa-Amino derivativesa-Alkoxy derivativesa-Thio derivativesAddition of aryl organometallicsIminium derivativesIntermolecular 1,2-additionN-Acyl anilinium derivativesN-Acyl piperidinium derivativesN-Acyl pyridinium derivativesN-Acyl isoquinolinium derivativesAuxiliary on nucleophilesIntramolecular 1,2-additionHydrazonesSimple alkyl/aryl aldehyde derivativesa-Amino and a-alkoxy substituted aldehyde derivativesa,a-Heteroatom substituted hydrazones (glyoxal and pyruvaldehyde derivatives)Auxiliary on nitrogenAuxiliary on carbonHydrazonium derivativesNitrone derivativesRADICAL ADDITIONHydrazonesOximesREFERENCESADDITION REACTIONS TO C=O BONDSREDUCTIONa-Alkoxy ketonesa-Keto aldehydes1,2-Diketonesa-Keto acid derivativesb-Aminoketonesb-Keto aldehydesb-Keto acid derivativesw-Keto acid derivativesENE REACTIONSWITTIG AND RELATED OLEFINATIONADDITION OF ORGANOMETALLIC AND RELATED REAGENTSAuxiliary-bearing acceptor carbonyl derivatives1,2-Dicarbonyl derivativesa-Oxo acid derivativesRelated aminals and acetals1,n-Hydroxycarbonyl derivatives1,n-Dicarbonyl derivativesw-Acyl carbonyl derivativesAuxiliary-bearing organometallic donor reagentsAcyl anion equivalents (formyl, acetyl, acryloyl, benzoyl)Allylic and benzylic related derivativesFormamidinesAromatic derivativesADDITION OF ENOLATES (ALDOL AND RELATED REACTIONS)Auxiliary-bearing acceptor carbonyl derivativesAuxiliary-bearing enolate equivalents from carbonyl precursorsCreation of a single stereocentreCreation of two stereocentresAuxiliary-bearing enolate equivalents from carboxylic acid precursorsAcetate equivalents - creation of a single stereocentreReaction with alkyl aldehydesReaction with a,b-unsaturated aldehydesReaction with aromatic aldehydesReaction with a- or b-heteroatom functionalized aldehydesReaction with ketonesPriopionate equivalents - creation of two stereocentresReaction with alkyl aldehydesReaction with a,b-unsaturated aldehydesReaction with aromatic aldehydesReaction with a- or b-heteroatom functionalized aldehydesReaction with ketonesHigher order equivalentsCreation of a single stereocentreCreation of two stereocentresPhenacyl and phenethyl derivativesOthersa,b- and b,g-Unsaturated acyl enolate equivalentsAcryloyl derivatives (Baylis-Hillman and related reactions)Crotonyl and related derivativesAuxiliary-bearing a-heteroacyl derivativesa-Amino acid derivatives - auxiliary bound to acyla-Amino acid derivatives - auxiliary bound to nitrogena-Amino acid derivatives - auxiliary on both acid and nitrogen (bislactim ethers / cyclic Schiff bases)a-Alkoxy derivativesa-Thio derivativesa-Halo derivativesHomoenolate equivalentsTANDEM REACTIONSRADICAL REACTIONSAddition to auxiliary-bearing acceptor carbonyl derivativesAddition by auxiliary-bearing donor radical derivativesIntramolecular additionCoupling reactionsREFERENCESCYCLOADDITIONS[2+2]-CYCLOADDITIONSPhotochemical reactionsIntermolecular cyclobutane formationIntramolecular cyclobutane formationOxetane formation (Paterno-Büchi reaction)Reactions of ketene-based derivativesReaction of ketenes with auxiliary-bearing alkenesReaction of ketene acetals/thioacetals with auxiliary-bearing alkenesReaction of auxiliary-bearing ketenes with imines (Staudinger reaction)Reaction of keteniminium derivatives with alkenesIntermolecular cyclobutanone formationIntramolecular cyclobutanone formation[3+2]-CYCLOADDITIONSPhotochemical reactionsAlkyl diazo dipoles - reaction with auxiliary-bearing C=C dipolarophilesNitrile oxide dipolesAlkyl nitrile oxide dipoles with C=C dipolarophilesAcrylic acid-derived dipolarophilesHigher order enoyl dipolarophilesVinyl ether dipolarophilesAryl nitrile oxide dipoles with C=C dipolarophilesAcrylic acid-derived dipolarophilesHigher order enoyl dipolarophilesVinyl ether dipolarophilesAryl nitrile oxide dipoles with C=N dipolarophilesAcyl and halo nitrile oxide dipolesNitrilimine dipoles - reaction with auxiliary-bearing C=C dipolarophilesNitrone dipolesAuxiliary on C=C dipolarophileAuxiliary on the nitrone dipoleSilyl nitronate dipoles - reaction with auxiliary-bearing C=C dipolarophilesAzomethine and related ylide dipolesAuxiliary on the C=C dipolarophileAcrylic acid derivativesHigher order enoyl derivativesAuxiliary on the ylide dipoleThiocarbonyl ylidesSundry transition metal-mediated equivalents[4+2]-INTERMOLECULAR HOMO-CYCLOADDITIONS (DIELS-ALDER REACTIONS) - AUXILIARY ON THE DIENOPHILEAcrylic acid derived dienophiles with acyclic dienesButadieneMonosubstituted butadienesDisubstituted butadienesAcrylic acid derived dienophiles with cyclic dienesCyclopentadienesCyclohexadienesHeterocyclic dienesMiscellaneous dienesMethacrylic acid derived dienophilesOther a- or b-substituted acrylic derived dienophilesAllene derived dienophilesCrotonic acid derived dienophilesAcyclic dienesCyclic dienesCinnamic and related aromatic acid derived dienophilesFumaric and maleic acid derived dienophilesAcyclic dienesCyclic dienesMiscellaneous acyl-derived dienophilesHeteroatom substituted non-acyl dienophiles (allyl amines/ethers)Cyclic dienophilesTandem processes[4+2]-INTERMOLECULAR HOMO-CYCLOADDITIONS (DIELS-ALDER REACTIONS) - AUXILIARY ON THE DIENEAcyclic dienes2,4-Pentdienoic acid derivativesN-functionalized dienes (enamine)N,O- functionalized dienes (enamine/enol ether)O- functionalized dienes (enol ether)O,O- functionalized dienes (ketene acetal/enol ether)S- functionalized dienes (sulfixyl)S,O- functionalized dienes (sulfinyl/enol ether)Cyclic dienes[4+2]-INTRAMOLECULAR HOMO-CYCLOADDITIONS (DIELS-ALDER REACTIONS)[4+2]-HETERO-CYCLOADDITIONS (HETERO-DIELS-ALDER REACTIONS)Auxiliary on dienophileN in heterodieneO in heterodieneS in heterodieneN/O in heterodieneN/S in heterodieneN/N/O in heterodieneAuxiliary on heterodienophileN in heterodienophileO in heterodienophileS in heterodienophileN/O in heterodienophileN/S in heterodienophileAuxiliary on dieneN in heterodienophileO in heterodienophileS in heterodienophileN/N in heterodienophileN/O in heterodienophileO/O in heterodienophileAuxiliary on heterodieneN in heterodieneO in heterodieneS in heterodieneN/O in heterodiene[4+3] CYCLOADDITIONS[6+2]- AND [6+4]-CYCLOADDITIONSREFERENCESREARRANGEMENTS[2,3]-SIGMATROPIC VARIANTSWittig rearrangementMeisenheimer rearrangementOther rearrangements[3,3]-SIGMATROPIC VARIANTSCarroll rearrangementClaisen rearrangementAza-Claisen rearrangementThia-Claisen rearrangementCope / oxy-Cope / siloxy-Cope rearrangementOther rearrangementsREFERENCESMISCELLANEOUS REACTIONSSUNDRY ENE REACTIONSTRANSITION-METAL CONTROLLED REACTIONSCarbene insertion reactionsC-H InsertionsN-H InsertionO-H InsertionSi-H InsertionCoupling reactionsCoupling of allyl derivativesCoupling of aryl derivativesCyclization reactionsHeck reactionsPauson-Khand reactionsMiscellaneous cyclizationsSulfoxide preparation from sulfidesElimination reactionsREFERENCES

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Key Features
* This remarkable major reference work is the first such compilation and represents the only total source for the diverse applications of auxiliaries
* Thoroughly cross-referenced to enable comparative selection of auxiliaries to be made dependent on target application
* Includes more than 13,000 auxiliary reaction applications with complete reaction details for each auxiliary
* Includes over 2,700 references, for reactions involving all recyclable chiral auxiliaries, published through mid-2000
* The material is compiled in a manner that facilitates its use as a reference source for practitioners of asymmetric organic synthesis in making an informed selection of an auxiliary for a specific application

About the Author

Greg Roos obtained his formal education, comprising of a BSc (1971), BSc Honours (1972), and PhD in Organic Synthesis (1976), at the University of Cape Town. A postdoctoral fellowship (1978) with Richard Cookson at the University of Southampton was followed by a few years of pharmaceutical industrial experience. His full-time academic career began at the University of Natal, Pietermaritzburg (1981-1994), and continued at Murdoch University, Perth, Australia (1994-1997). This was followed by an extended period in the Middle East, including Sultan Qaboos University, Oman (1998-2004) and The Petroleum Institute, Abu Dhabi (2004-2008). He has successfully taught across various cultures and has received awards for his teaching contributions and innovations. Currently, as an adjunct Professor at Murdoch University (since 2009), he now shares his time between Perth and Dubai. His research interests have focused on the development of synthetic methodology, with particular interest in asymmetric processes. This led to numerous publications and conference contributions in the areas of the Baylis-Hillman reaction, imidazolidinone chiral auxiliaries, and dirhodium catalyst development and applications. This period also included a number of collaborative research visits with Tony McKervey (University College Cork & Queen's University, Belfast), C. K. Sha (Shin Hua University, Taiwan), Mike Doyle (Trinity University, San Antonio), and Ron Warrener (CQU Rockhampton, Queensland). In 2001, he received the Merck Gold Medal for research from the South African Chemical Institute.