Comprehensive organic synthesis : selectivity, strategy & efficiency in modern organic chemistry

Author(s)

• Trost, Barry M.
• Fleming, Ian

Bibliographic Information

Comprehensive organic synthesis : selectivity, strategy & efficiency in modern organic chemistry

editor-in-chief, Barry M. Trost ; deputy editor-in-chief, Ian Fleming

Pergamon Press, 1991

• : set
• v. 1
• v. 2
• v. 3
• v. 4
• v. 5
• v. 6
• v. 7
• v. 8
• v. 9

Note

v. 1-2. Additions to C-X π-bonds, pt. 1-2 -- v. 3. Carbon-carbon σ-bond formation -- v. 4. Additions to and substitutions at C-C π-bonds -- v. 5. Combining C-C π-bonds -- v. 6. Heteroatom manipulation -- v. 7. Oxidation -- v. 8. Reduction -- v. 9. Cumulative indexes

Description and Table of Contents

Volume

: set ISBN 9780080359298

Description

The development of more effective routes to known materials and the production of new materials are important goals in many areas, including electronics, agriculture, medicine and textiles. Organic synthesis is central to achieving these goals. Comprehensive Organic Synthesisdraws together the common themes that underlie the many apparently disparate areas of organic chemistry which underpin synthetic strategies, thus providing a comprehensive overview of this important discipline.The contributions have been organized to reflect the way in which synthetic chemists approach a problem. In terms of organic molecules, the work is divided into formation of carbon-carbon bonds, introduction of heteroatoms and heteroatom interconversions. Thus, Volumes 1-5 focus on carbon-carbon formation, but also include aspects of heteroatom introduction. Volumes 6-8 concentrate on interconversion of heteroatoms, but also deal with exchange of carbon-carbon bonds for carbon-heteroatom bonds. Organization of the chapters is along the theme of selectivity, which is a critical question in determining the suitability of a synthetic method. Volume 9 contains cumulative author and subject indexes.Comprehensive Organic Synthesis will appeal to a wide audience. The set will be an essential reference work for all those seeking information on the solution of synthetic problems, whether they be experienced practitioners or chemists whose major interests lie outside organic synthesis. In addition, synthetic chemists requiring the essential facts in new areas, as well as students completely new to the field, will find Comprehensive Organic Synthesis an invaluable source, providing authoritative accounts of the essential facts and concepts.

Table of Contents

Selected contents: 1. Additions to C-X -Bonds, Part 1. Nonstabilized carbanion equivalents. Heteroatom-stabilized carbanion equivalents. Transformation of the carbonyl group into nonhydroxylic groups. Author index. Subject index. 2. Additions to C-X -Bonds, Part 2. Uncatalyzed additions of nucleophilic alkenes to C=X. Catalyzed additions of nulceophilic alkenes to C=X. Addition-elimination reactions (acylations). Additions of nucleophilic alkenes to C=NR and C=NR2+. Author index. Subject index. 3. Carbon-Carbon -Bond Formation. Alkylation of carbon. Coupling reactions. Rearrangement reactions. Other carbon-carbon bond forming reactions. Author index. Subject index. 4. Additions to and Substitutions at C-C -Bonds. Polar additions to activated alkenes and alkynes. Nucleophilic aromatic substitutions. Polar additions to alkenes and alkynes. Nonpolar additions to alkenes and alkynes. Author index. Subject index. 5. Combining C-C -Bonds. Ene reactions. [2+2] cycloadditions. [3+2] cycloadditions. [4+2] cycloadditions. Higher-order cycloadditions. Electrocyclic processes. Sigmatropic processes. Small-ring rearrangements. Other transition metal associated reactions. Author index. Subject index. 6. Heteroatom Manipulation. Displacement by substitution processes. Acylation-type reactions. Protecting groups. Functional group interconversion. Elimination reactions. Author index. Subject index. 7. Oxidation. Oxidation of unactivated C-H bonds. Oxidation of activated C-H bonds. Oxidation of C=C bonds. Oxidation of C-X bonds. Oxidation of C-C bonds. Oxidation of heteroatoms. Special topics. Author index. Subject index. 8. Reduction. Reduction of C=X bonds. Reduction of X=Y bonds. Reduction of C=C and C C bonds. Reduction of C-X to C-H. Author index. Subject index. 9. Indexes. Cumulative author index. Cumulative subject index.

Volume

v. 1 ISBN 9780080405926

Description

Volume 1 provides a detailed survey of reactions that entail the 1,2-addition of nonstabilized carbanion equivalents of carbonyl, imino and thiocarbonyl functionality. Emphasis has been placed on those reagents that result in highly selective addition reactions. Methods are reported to select, for example, one carbonyl group over another in the same molecule, or to add preferentially a fragment to one (enantiotopic of diastereotopic) face of a carbonyl group. Processes that result from an initial addition to the C=X functional group, for example alkenations and rearrangements, are also covered in this volume.

Table of Contents

Nonstabilized Carbanion Equivalents. Carbanions of alkali and alkaline earth cations: (i) synthesis and structural characterization. Carbanions of alkali and alkaline earth cations: (ii) selectivity of carbonyl addition reactions. Organoaluminum reagents. Organocopper reagents. Organo-titanium and organo-zirconium reagents. Organochromium reagents. Organo-zinc, -cadmium and -mercury reagents. Organocerium reagents. Samarium and ytterbium reagents. Lewis acid carbonyl complexation. Lewis acid promoted addition reactions of organometallic compounds. Nucleophilic addition to imines and imine derivatives. Nucleophilic addition to carboxylic acid derivatives. Heteroatom-Stabilized Carbanion Equivalents. Nitrogen stabilization. Boron stabilization. Sulfur stabilization. The Benzoin and related reactions. Silicon stabilization. Selenium stabilization. Transformation of the Carbonyl Group into Nonhydroxylic Groups. Alkene synthesis. Epoxidation and related processes. Skeletal reorganizations: chain extension and ring expansion. Author index. Subject index.

Volume

v. 2 ISBN 9780080405933

Description

Volume 2 deals mainly with the addition reactions of delocalized carbanions (enolates) and their synthetic relatives (metalloenamines, enol ethers, allyl organometallics) with carbonyl compounds, imines and iminium ions. Major emphasis is placed on C-C bond-forming reactions such as the aldol and Mannich reactions. Acylation reactions are also included in this volume. Several topics that have not previously been reviewed are covered, including the use of enzymatic aldol reactions in synthesis and the Passerini-Ugi reactions.

Table of Contents

Selected chapters: Uncatalyzed Additions of Nucleophilic Alkenes to C=X. Allyl organometallics. Heteroatom-stabilized allylic anions. Propargyl and allenyl organometallics. The Aldol reaction: general acid and base catalysis. The Aldol reaction: group I and group II enolates. The Aldol reaction: group III enolates. Zinc enolates: the Reformatsky and Blaise Reactions. The Aldol reaction: transition metal enolates. The Knoevenagel reaction. The Perkin reaction. Darzens' glycidic ester condensation. Use of enzymatic Aldol reactions in synthesis. Metalloenamines. Hydrazone anions. Catalyzed Additions of Nucleophilic Alkenes to C=X. The Prins and related reactions. Allylsilanes, allylstannanes and related systems. Asymmetric synthesis with enol ethers. Reactions of activated dienes with aldehydes. Addition-Elimination Reactions (Acylations). The aliphatic Friedel-Crafts reaction. The biomolecular aromatic Friedel-Crafts reaction. The Reimer-Tiemann reaction. The Vilsmeier-Haack reaction. Acylation of esters, ketones and nitriles. The Eschenmoser coupling reaction. Additions of Nucleophilic Alkenes to C=NR and C=NR2+. The bimolecular aliphatic Mannich and related reactions. The bimolecular aromatic Mannich reaction. The intramolecular Mannich and related reactions. Additions to N-acyliminium ions. The Passerini and Ugi reactions. Author index. Subject index.

Volume

v. 3 ISBN 9780080405940

Description

Volume 3 covers carbon-to-carbon single bond forming reactions involving sp3, sp2 and sp carbon centers, but only those which do not involve additions to C-X -bonds. The volume first compares and contrasts the alkylation reactions of all types of sp3 carbon nucleophiles and also covers vinyl and alkynyl carbanions. Following on from Volume 2, a separate section covers Friedel-Crafts alkylation reactions, which is complemented by discussions of polyene cyclizations and electrophilic transannular cyclizations in synthesis. Coupling reactions leading to -bond formation, and involving all types of combinations ofsp3, sp2 and sp carbon centers are next covered, including those reactions based on pinacol, acyloin and phenol oxidative coupling reactions, and also the Kolbe reaction. Rearrangement reactions, leading to carbon-to-carbon -bond formation, are often used in a clever manner in synthesis. The volume includes all those rearrangement reactions based on intermediate carbonium ions and carbanions, and also includes the benzil-benzilic acid and the Wolff rearrangements. The volume closes with coverage of carbonylation reactions, and the use of carbene insertion reactions into the C-H bond in synthesis.

Table of Contents

Alkylation of Carbon. Alkylations of enols and enolates. Alkylations of nitrogen-stabilized carbanions. Alkylations of sulphur-and selenium-stabilized carbanions. Alkylations of other heteroatom-stabilized carbanions. Alkylations of nonstabilized carbanions. Alkylations of vinyl carbanions. Alkylations of alkynyl carbanions. Friedel-Crafts alkylations. Polyene cyclizations. Transannular electrophilic cyclizations. Coupling Reactions. Coupling reactions between sp3 carbon centers. Coupling reactions between sp3 and sp2 carbon centers. Coupling reactions between sp2 carbon centers. Coupling reactions between sp2 and sp carbon centers. Coupling reactions between sp carbon centers. Pinacol coupling reactions. Acyloin coupling reactions. Kolbe reactions. Oxidative coupling of phenols and phenol ethers. Rearrangement Reactions. Wagner-Meerwein rearrangements. The Pinacol rearrangement. Acid-catalyzed rearrangements of epoxides. The semipinacol and other rearrangements. Dienone-phenol rearrangements and related reactions. Benzil-benzilic acid rearrangements. The Favorskii rearrangement. The Ramberg-Backlund rearrangement. The Wolff rearrangement. The Stevens and related rearrangements. The Wittig rearrangement. Other Carbon-Carbon Bond Forming Reactions. Carbonylation and decarbonylation reactions. Carbon-carbon bond formation by C-H insertion. Author index. Subject index.

Volume

v. 4 ISBN 9780080405957

Description

Volume 4 focuses on additions and the resulting substitutions at carbon-carbon -bonds. Part 1 includes processes generally considered as simple polar reactions, reactive electrophiles and nucleophiles adding to alkenes and alkynes. A major topic is Michael-type addition to electron deficient -bonds, featured in the first six chapters. In part 2 are collected the four general processes leading to nucleophilic aromatic substitution, including radical chain processes and transition metal activation through to -complexation. Metal-activated addition (generally by nucleophiles) to alkenes and polyenes is presented in part 3, including allylic alkylation catalyzed by palladium. The coverage of nonpolar additions in part 4 includes radical additions, organometal addition (Heck reaction), carbene addition, and 1,3-dipolar cycloadditions.

Table of Contents

Polar Additions to Activated Alkenes and Alkynes. Stabilized nucleophiles with electron deficient alkenes and alkynes. Conjugate additions of reactive carbanions to activated alkenes and alkynes. Conjugate additions of carbon ligands to activated alkenes and alkynes mediated by Lewis acids. Organocuprates in the conjugate addition reaction. Asymmetric nucleophilic addition to electron deficient alkenes. Nucleophilic addition-electrophilic coupling with a carbanion intermediate. Addition of H-X reagents to alkenes and alkynes. Electrophilic addition of X-Y reagents to alkenes and alkynes. Electrophilic heteroatom cyclizations. Nucleophilic Aromatic Substitutions. Arene substitution via nucleophilic addition to electron deficient arenes. Nucleophilic coupling with aryl radicals. Nucleophilic coupling with arynes. Nucleophilic addition to arene-metal complexes. Polar Additions to Alkenes and Alkynes. Heteroatom nucleophiles with metal-activated alkenes and alkynes. Carbon nucleophiles with alkenes and alkynes. Nucleophiles with allyl-metal complexes. Nucleophiles with cationic pentadienyl-metal complexes. Carbon electrophiles with dienes and polyenes promoted by transition metals. Nonpolar Additions to Alkenes and Alkynes. Radical addition reactions. Radical cyclizations and sequential radical reactions. Vinyl substitutions with organopalladium intermediates. Carbometallation of alkenes and alkynes. Hydroformylation and related additions of carbon monoxide to alkenes and alkynes. Methylene and nonfunctionalized alkylidene transfer to form cyclopropanes. Formation and further transformations of 1,1-dihalocyclopropanes. Addition of ketocarbenes to alkenes, alkynes and aromatic systems. Intermolecular 1,3-dipolar cycloadditions. Intramolecular 1,3-dipolar cycloadditions. Author index. Subject index.

Volume

v. 5 ISBN 9780080405964

Description

The guiding principle underlying the subject matter specifically compiled in Volume 5 has been to make available to the organic chemical community a sourcebook comprehensively covering all the important -bond-dependent transformations. Thermal, photochemical, and metal-catalyzed cycloadditions of every major type are expertly detailed by the most knowledgeable researchers in these areas. The synthetically useful electrocyclic and sigmatropic processes where alkenic centers are intimately involved in the structural change are similarly canvassed in compact detail. With added attention given to ene reactions, small-ring rearrangements, and related transition metal-associated reactions, coverage has been achieved of the full range of organic transformations directly involving the rebonding of alkenic centers. As a consequence, this volume should serve as the comprehensive sourcebook of the field for the next decade and beyond.

Table of Contents

Selected contents: Ene Reactions. Ene reactions with alkenes as enophiles. Metallo-ene reactions. [2 + 2] Cycloadditions. Thermal cyclobutane ring formation. Formation of four-membered heterocycles. Di- -methane photoisomerizations. Oxa-di- -methane photoisomerizations. [3 + 2] Cycloadditions. Thermal cycloadditions. Transition metal mediated cycloadditions. [4 + 2] Cycloadditions. Intermolecular Diels-Alder reactions. Retrograde Diels-Alder reactions. Higher-Order Cycloadditions. [4 + 3] cycloadditions. [4 + 4] and [6 + 4] cycloadditions. [3 + 2] and [5 + 2] arene-alkene photocyloadditions. Electrocyclic Processes. Cyclobutene ring opening reactions. 1,3-cyclohexadiene formation reactions. Nazarov and related cationic cyclizations. Sigmatropic Processes. Cope, oxy-cope and anionic oxy-cope rearrangements. Claisen rearrangements. Consecutive rearrangements. Small-Ring Rearrangements. Rearrangements of vinylcyclopropanes and related systems. Charge-accelerated rearrangements. Other Transition Metal Associated Reactions. The Pauson-Khand reaction. Metal-carbene cycloadditions. Metal-catalyzed cycloaddition of small ring compounds. Author index. Subject index.

Volume

v. 6 ISBN 9780080405971

Description

In this volume, those functional groups containing heteroatoms that have gained importance in organic synthesis are dealt with in detail. The introduction of these various groups and their relevant transformations are described and the various aspects of chemoselectivity, regioselectivity and stereoselectivity are discussed. After a compilation of the synthetically most useful substitution processes, there is a series of chapters on the various types of acylation reactions and in this context the different methods of acyl group activation are discussed. As functional group protection is of very general importance for organic synthesis, a corresponding chapter is included. This is followed by a section on the preparation of carbonyl derivatives and the most important transformations and rearrangements of functional group derivatives. At the end of the volume one finds chapters on all types of elimination reactions and related thermal reactions together with a survey on fragmentation processes in organic synthesis.

Table of Contents

Displacement by Substitution Processes. Synthesis of alcohols and ethers. Synthesis of glycosides. Synthesis of amines and ammonium salts. Synthesis of nitroso, nitro and related compounds. Synthesis of sulfides, sulfoxides and sulfones. Synthesis of phosphonium ylides. Synthesis of halides. Formation of pseudohalides, nitriles and related compounds. Ritter-type reactions. Acylation-Type Reactions. Synthesis of acid halides, anhydrides and related compounds. Synthesis of activated esters and related compounds. Synthesis of amides and related compounds. Synthesis of thioamides and thiolactams. Synthesis of thioesters and thiolactones. Selenoesters of all oxidation states. Synthesis of iminium salts, orthoesters and related compounds. Inorganic acid derivatives. Protecting Groups. Alcohols, amines and thiols, including multiple protecting groups. Functional Group Interconversion. Carbonyl group derivatization. Use of carbonyl derivatives for heterocyclic synthesis. Functional group transformations via carbonyl derivatives. Degradation reactions. Functional group transformation via allyl rearrangement. 2,3-sigmatropic rearrangements. Polonovski- and Pummerer-type reactions and the Nef reaction. Elimination Reactions. Eliminations to form alkenes, allenes and alkynes and related reactions. Reductive elimination, vicinal deoxygenation and vicinal desilylation. The Cope elimination, sulfoxide elimination and related thermal reactions. Fragmentation reactions. Author index. Subject index.

Volume

v. 7 ISBN 9780080405988

Description

This volume covers all methods of oxidation for use in organic synthesis. Emphasis has been placed on selectivity and functional group compatibility together with practical utility and applications. The volume is broadly divided to cover oxidation of unactivated carbon-hydrogen bonds, oxidation of activated carbon-hydrogen bonds, that is to say those adjacent to activating substituents and adjacent to heteroatoms, and oxidation of carbon-carbon double bonds. The volume also covers oxidation of C-X bonds, carbon-carbon single bonds, heteroatom oxidation and a number of special topics such as electrochemical methods, oxidative rearrangements, solid supported reagents, electron transfer oxidation, and biological methods.

Table of Contents

Selected contents: Oxidation of Unactivated C-H Bonds. Oxidation by chemical methods. Oxidation by nitrene insertion. Oxidation by microbial methods. Oxidation of Activated C-H Bonds. Oxidation adjacent to C=C bonds. Oxidation adjacent to sulfur. Oxidation adjacent to nitrogen. Oxidation adjacent to oxygen of ethers. Oxidation adjacent to oxygen of alcohols by other methods. Synthesis of quinones. Oxidation of C=C Bonds. Addition reactions with formation of carbon-oxygen bonds: (i) General methods of epoxidation. Addition reactions with formation of carbon-oxygen bonds: (iv) The Wacker oxidation and related reactions. Addition reactions with formation of carbon-nitrogen bonds. Cleavage reactions. Oxidation of C-X Bonds. Oxidation of carbon-boron bonds. Oxidation of carbon-metal bonds. Oxidation of carbon-halogen bonds. Oxidation of C-C Bonds. The Baeyer-Villiger reaction. The Beckmann and related reactions. Glycol cleavage reactions. Oxidation of Heteroatoms. Oxidation of nitrogen and phosphorus. Oxidation of sulfur, selenium and tellurium. Special Topics. Oxidation by electrochemical methods. Oxidative rearrangement reactions. Electron transfer oxidation. Author index. Subject index.

Volume

v. 8 ISBN 9780080405995

Description

This volume contains 37 chapters on methods for reducing functional groups, organized into four main parts. (i) Reduction of C=X systems, where X is an electronegative heteroatom, divided into 14 chapters based on the degree of reduction, the oxidation level of the C=X substrate, and on the nature of the reagent. (ii) Reduction of X=Y systems, divided into three chapters, covering the reduction of such groups as nitro, azo, and the various kinds of P=O and S=O groups. (iii) Reduction of C=C and C C, divided into 12 chapters based on the method of reduction, with aromatic, heteroaromatic, and conjugated systems treated separately, and including an extensive discussion of hydrometallation. (iv) Reduction of single bonds, C-X to C-H, in eight chapters, including the hydrogenolysis of the various kinds of C-X bonds, the reduction of epoxides, and the reduction of vinyl derivatives to alkenes. Each chapter includes a discussion of chemoselectivity, regioselectivity, and stereoselectivity, wherever it is appropriate, and most include advice on the reagent of choice, and the mechanistic basis of the various methods of reduction. In short, it is, within the space available, as near to a comprehensive account of reduction in organic chemistry as one could hope for.

Table of Contents

Selected contents: Reduction of C=X Bonds. Reduction of C=O to CHOH by metal hydrides. Reduction of C=N to CHNH by metal hydrides. Reduction of C=X to CHXH by hydride delivery from carbon. Reduction of C=X to CHXH by dissolving metals and related methods. Reduction of C=X to CHXH by catalytic hydrogenation. Reduction of carboxylic acids to alcohols, ethers and amines. Reduction of carboxylic acids to aldehydes by metal hydrides. Reduction of carboxylic acids to aldehydes by other methods. Reduction of C=X to CH2 by dissolving metals and related methods. Reduction of X=Y Bonds. Reduction of nitro and nitroso compounds. Reduction of N=N, N-N, N-O and O-O bonds. Reduction of S=O and SO2 to S, of P=O to P, and of S-X to SH. Reduction of C=C and C C Bonds. Heterogeneous catalytic hydrogenation of C=C and C C. Homogeneous catalytic hydrogenation of C=C and C C. Reduction of C=C and C C by noncatalytic chemical methods. Partial and complete reduction of pyridines and their benzo analogs. Hydrozirconation of C=C and C C, and hydrometallation by other metals. Hydroboration of C=C and C C. Hydroalumination of C=C and C C. Hydrosilylation of C=C and C C. Reductions of C-X to C-H. Reduction of saturated alkyl halides to alkanes. Reduction of saturated alcohols and amines to alkenes. Reduction of epoxides. Reduction of ketones to alkenes. Hydrogenolysis of allyl and benzyl halides and related compounds. Reduction of -substituted carbonyl compounds-CX-CO- to carbonyl compounds -CH-CO-. Author index. Subject index.

Volume

v. 9 ISBN 9780080406008

Table of Contents

Cumulative author index. Cumulative subject index.

by "Nielsen BookData"

Details

• NCID: BA13431224
• ISBN:
  • 0080359299
  • 0080405924
  • 0080405932
  • 0080405940
  • 0080405959
  • 0080405967
  • 0080405975
  • 0080405983
  • 0080405991
  • 0080406009
• LCCN: 90026621
• Country Code: uk
• Title Language Code: eng
• Text Language Code: eng
• Place of Publication: Oxford
• Pages/Volumes: 9 v.
• Size: 28 cm
• Classification:
  • NDLC : PA325
  • DC20 : 547.2
  • LCC : QD262
  • NDC8 : 434
• Subject Headings:
  • LCSH : Organic compounds -- Synthesis