Science of Synthesis

Science of Synthesis is the authoritative and comprehensive reference work for the entire field of organic and organometallic synthesis.

Science of Synthesis presents the important synthetic methods for all classes of compounds and includes:

Methods critically evaluated by leading scientists

Background information and detailed experimental procedures

Schemes and tables which illustrate the reaction scope

Preface

As the pace and breadth of research intensifies, organic synthesis is playing an increasingly central role in the discovery process within all imaginable areas of science: from pharmaceuticals, agrochemicals, and materials science to areas of biology and physics, the most impactful investigations are becoming more and more molecular. As an enabling science, synthetic organic chemistry is uniquely poised to provide access to compounds with exciting and valuable new properties. Organic molecules of extreme complexity can, given expert knowledge, be prepared with exquisite efficiency and selectivity, allowing virtually any phenomenon to be probed at levels never before imagined. With ready access to materials of remarkable structural diversity, critical studies can be conducted that reveal the intimate workings of chemical, biological, or physical processes with stunning detail.

The sheer variety of chemical structural space required for these investigations and the design elements necessary to assemble molecular targets of increasing intricacy place extraordinary demands on the individual synthetic methods used. They must be robust and provide reliably high yields on both small and large scales, have broad applicability, and exhibit high selectivity. Increasingly, synthetic approaches to organic molecules must take into account environmental sustainability. Thus, atom economy and the overall environmental impact of the transformations are taking on increased importance.

The need to provide a dependable source of information on evaluated synthetic methods in organic chemistry embracing these characteristics was first acknowledged over 100 years ago, when the highly regarded reference source Houben–Weyl Methoden der Organischen Chemie was first introduced. Recognizing the necessity to provide a modernized, comprehensive, and critical assessment of synthetic organic chemistry, in 2000 Thieme launched Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. This effort, assembled by almost 1000 leading experts from both industry and academia, provides a balanced and critical analysis of the entire literature from the early 1800s until the year of publication. The accompanying online version of Science of Synthesis provides text, structure, substructure, and reaction searching capabilities by a powerful, yet easy-to-use, intuitive interface.

From 2010 onward, Science of Synthesis is being updated quarterly with high-quality content via Science of Synthesis Knowledge Updates. The goal of the Science of Synthesis Knowledge Updates is to provide a continuous review of the field of synthetic organic chemistry, with an eye toward evaluating and analyzing significant new developments in synthetic methods. A list of stringent criteria for inclusion of each synthetic transformation ensures that only the best and most reliable synthetic methods are incorporated. These efforts guarantee that Science of Synthesis will continue to be the most up-to-date electronic database available for the documentation of validated synthetic methods.

Also from 2010, Science of Synthesis includes the Science of Synthesis Reference Library, comprising volumes covering special topics of organic chemistry in a modular fashion, with six main classifications: (1) Classical, (2) Advances, (3) Transformations, (4) Applications, (5) Structures, and (6) Techniques. Titles will include Stereoselective Synthesis, Water in Organic Synthesis, and Asymmetric Organocatalysis, among others. With expertevaluated content focusing on subjects of particular current interest, the Science of Synthesis Reference Library complements the Science of Synthesis Knowledge Updates, to make Science of Synthesis the complete information source for the modern synthetic chemist.

The overarching goal of the Science of Synthesis Editorial Board is to make the suite of Science of Synthesis resources the first and foremost focal point for critically evaluated information on chemical transformations for those individuals involved in the design and construction of organic molecules.

Throughout the years, the chemical community has benefited tremendously from the outstanding contribution of hundreds of highly dedicated expert authors who have devoted their energies and intellectual capital to these projects. We thank all of these individuals for the heroic efforts they have made throughout the entire publication process to make Science of Synthesis a reference work of the highest integrity and quality.

The Editorial Board

July 2010

E. M. Carreira (Zurich, Switzerland)

C. P. Decicco (Princeton, USA)

A. Fuerstner (Muelheim, Germany)

G. A. Molander (Philadelphia, USA)

P. J. Reider (Princeton, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

M. Shibasaki (Tokyo, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Abstracts

2.4.12 Arene Organometallic Complexes of Chromium, Molybdenum, and Tungsten

M. Uemura

This review is an update to Section 2.4 and covers the literature from 1999 to 2010. (η⁶-Arene)chromium complexes have been considerably developed in organic synthesis on the basis of the strong electron-withdrawing ability and steric effect of the tricarbonylchromium fragment. The corresponding arenechromium complexes of unsymmetrical 1,2- or 1,3-disubstituted arene ligands are nonsuperimposable on their mirror images. Catalytic asymmetric synthesis of the planar chiral arenechromium complexes with chiral catalysts has been actively developed. The planar chiral arenetricarbonylchromium complexes have been widely employed in asymmetric synthesis, natural product synthesis, and increasingly as chiral ligands in asymmetric catalysis. This review focuses on the synthesis of planar chiral arenechromium complexes, and their applications in organic synthesis.

Keywords: asymmetric hydroboration · asymmetric reduction of ketones · atropisomer · catalytic asymmetric synthesis · chromium migration · cross coupling · cycloisomerization · enantioselective lithiation · gold catalysts · higher-order cycloaddition · nucleophilic substitution · molecular switch · axially chiral biaryl · palladium catalyst · planar chirality · radical coupling

4.4.26.7 1-Diazo-1-silylalkanes

Y. Hari, T. Aoyama, and T. Shioiri

This manuscript is an update to Section 4.4.26 describing methods for the synthesis and applications of 1-diazo-1-silylalkanes. This update focuses on papers published in the period 1999–2010.

Keywords: silyldiazoalkanes · diazo(trimethylsilyl)methane · alkylidene carbenes · Colvin rearrangement · insertion reaction · cyclopropanation · [3 + 2] cycloaddition · diazo(silyl)acetates · diazo(silyl)methyl ketones

7.1.2.44 Aluminum Hydrides

H. Naka and S. Saito

This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the preparation of aluminum hydrides used for organic synthesis, and recent advances in synthetic applications of aluminum hydrides. Various chemoselective reductions, such as partial reduction of esters, nitriles, or amides to aldehydes, are possible using aluminum hydrides with suitable ligands.

Keywords: aluminum compounds · chemoselectivity · hydroalumination · metal hydrides · reduction · reductive cyclization · regioselectivity · stereoselective synthesis

7.1.3.18 Aluminum Halides

H. Naka and S. Saito

This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the preparation of aluminum halides used for organic synthesis, along with recent synthetic applications of aluminum halides.

Keywords: acid catalysts · aluminum compounds · bromides · chiral compounds · chlorides · halides · iodides · ionic liquids · Lewis acid catalysts · salen complexes

7.1.9.11 Triorganoaluminum Compounds

M. Oishi and H. Takikawa

This manuscript is an update to the earlier Science of Synthesis contribution describing applications of triorganoaluminums and related compounds. It focuses on selective carboalumination, catalytic enantioselective conjugate additions, and carbonyl additions covered in the literature over the period 2004–2010. In addition, activations of C—F and C—H bonds are of increasing importance in organoaluminum chemistry.

Keywords: carboalumination · carbonyl additions · conjugate addition reactions · coupling reactions · regioselectivity · enantioselectivity · C—H bond activation · C—F bond activation

7.2.8 Gallium Compounds

M. Yamaguchi

This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of organogallium compounds as well as their application in organic synthesis. It focuses on the literature published in the period 2002–2010.

Keywords: catalysis · complexation · gallium compounds · Lewis acid catalysts · metal alkyl complexes · organometallic reagents · oxidative addition

7.3 Product Class 3: Indium Compounds

S. Araki and T. Hirashita

This manuscript is a revision update to the earlier Science of Synthesis contribution describing methods for the synthesis of indium compounds. More recent developments in this area, in particular chemical transformations using indium reagents, have been reviewed.

Keywords: allylic compounds · allenic compounds · allylation · Barbier reaction · carbon—metal bonds · carbon–carbon coupling reactions · indium compounds · Lewis acid catalysts · transmetalation

7.9.5 Barium Compounds

A. Yanagisawa

This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the application of barium compounds in organic synthesis. It focuses on the literature published in the decade up to 2010.

Keywords: aldol reaction · β-amino carbonyl compounds · asymmetric catalysis · barium compounds · conjugate addition · cross-coupling reactions · Diels–Alder reaction · 1,5-diketones · homocoupling · β-hydroxy carbonyl compounds · Mannich-type reaction · propargylic compounds

8.1.28 The Catalytic Use of Lithium Compounds for Bond Formation

S. Matsunaga

The catalytic use of lithium compounds as Lewis bases and Brønsted bases is introduced. Several C—C bond-forming (enantioselective) transformations, such as aldol reactions, Mannich reactions, cyanation, conjugate additions, sulfur ylide additions for oxirane and oxetane synthesis, and others, are described.

Keywords: asymmetric aldol reaction · asymmetric Mannich reaction · asymmetric cyanation · lithium compounds · Lewis base catalysts · asymmetric conjugate addition reactions · asymmetric Michael reaction · sulfur ylides · oxetane · oxiranes · Brønsted base catalysts

8.2.16 The Catalytic Use of Sodium Compounds for Bond Formation

T. Arai

Safe and inexpensive sodium reagents are promoted as versatile Lewis base, Lewis acid, and combination acid–base catalysts in green chemistry. Sodium-containing heterobimetallic asymmetric complexes enable highly stereoselective catalysis of transformations such as Michael reactions, cyclopropanation, and the Henry reaction.

Keywords: sodium compounds · catalysis · asymmetric synthesis · Mukaiyama reaction · Michael reaction

16.8.5 Pyridazines

J. Zhang

This manuscript is an update of the original Science of Synthesis chapter and includes methods for the preparation of pyridazines and pyridazinones described in the literature up to 2010. Methods proceeding by condensation of diketones, keto acids, or keto esters with hydrazine, and Diels–Alder reaction of 1,2,4,5-tetrazines and ketones are covered, as well as the application of halopyridazines in palladium-catalyzed cross-coupling reactions.

Keywords: pyridazines · ring closure · condensation reactions · dicarbonyl compounds · Diels–Alder reaction · cross-coupling reactions

20.2.1.8.13 Synthesis with Retention of the Functional Group (Update 1)

G. Landelle and J.-F. Paquin

This manuscript is an update to the earlier Science of Synthesis contribution, and specifically describes methods involving conjugate addition to α,β-unsaturated carboxylic acids. It focuses on the literature published in the period 1982–2009.

Keywords: conjugate addition · carboxylic acids · unsaturated compounds · organometallic reagents · stereoselectivity · regioselectivity

20.2.1.8.14 Synthesis with Retention of the Functional Group (Update 2)

J. L. Gleason and E. A. Tiong

This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of carboxylic acids. It focuses on direct α-alkylations of carboxylic acids and diastereoselective α-alkylation of carboxylic acid derivatives used in carboxylic acid synthesis.

Keywords: alkylation · carboxylic acid · chiral auxiliary · enolates · alkyl halides · tertiary stereocenters · quaternary stereocenters

21.15 Product Class 15: Polyamides

T. Higashihara and M. Ueda

This manuscript describes methods for the synthesis of polyamides, especially focusing on recent advances in aromatic polyamides as well as synthesis of block copolymers, hyperbranched polymers, and dendrimers.

Keywords: amides · condensation reactions · dendrimers · diamines · dicarboxylic acids · polymerization · polymers

27.13.3 Nitrones and Cyclic Analogues

P. Merino

This chapter is an update to the previous Science of Synthesis contribution describing methods for the synthesis of nitrones and cyclic analogues. It covers the literature published in the period 2004–2010.

Keywords: nitrones · hydroxylamines · amines · imines · oxidation · isoxazolidines · carbon—nitrogen bonds · dipolar cycloaddition · nucleophilic addition · nitrogen heterocycles

40.1.1.1.2 Reductive Amination of Carbonyl Compounds

P. Margaretha

This chapter summarizes syntheses of both achiral and chiral amines, either via direct reductive amination of carbonyl compounds or by two-step reactions, wherein the first step consists of conversion of the carbonyl compound into an N-derivative (N-alkylidenealkylamine, enamine, imine, oxime, or oxime ether), which, in the second step, is then reduced to the desired amine product. It is shown that primary, secondary, and tertiary amines are easily accessible synthetic targets. Neither N-protected amines (e.g., amides) nor amines containing a functional group of higher priority (e.g., amino acids) are taken into account in this survey.

Keywords: amination · amines · N-alkylidenealkylamines · enamines · imines · oximes · oxime ethers · carbonyl compounds · reduction · enantioselective reactions

Science of Synthesis Knowledge Updates 2010/4

Preface

Abstracts

Table of Contents

2.4.12 Arene Organometallic Complexes of Chromium, Molybdenum, and Tungsten (Update 2010)

M. Uemura

4.4.26.7 1-Diazo-1-silylalkanes (Update 2010)

Y. Hari, T. Aoyama, and T. Shioiri

7.1.2.44 Aluminum Hydrides (Update 2010)

H. Naka and S. Saito

7.1.3.18 Aluminum Halides (Update 2010)

H. Naka and S. Saito

7.1.9.11 Triorganoaluminum Compounds (Update 2010)

M. Oishi and H. Takikawa

7.2.8 Gallium Compounds (Update 2010)

M. Yamaguchi

7.3 Product Class 3: Indium Compounds

S. Araki and T. Hirashita

7.9.5 Barium Compounds (Update 2010)

A. Yanagisawa

8.1.28 The Catalytic Use of Lithium Compounds for Bond Formation

S. Matsunaga

8.2.16 The Catalytic Use of Sodium Compounds for Bond Formation

T. Arai

16.8.5 Pyridazines (Update 2010)

J. Zhang

20.2.1.8.13 Synthesis with Retention of the Functional Group (Update 1, 2010)

G. Landelle and J.-F. Paquin

20.2.1.8.14 Synthesis with Retention of the Functional Group (Update 2, 2010)

J. L. Gleason and E. A. Tiong

21.15 Product Class 15: Polyamides

T. Higashihara and M. Ueda

27.13.3 Nitrones and Cyclic Analogues (Update 2010)

P. Merino

40.1.1.1.2 Reductive Amination of Carbonyl Compounds

P. Margaretha

Author Index

Abbreviations

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