Enantiopure cyanohydrins and β-nitro alcohols serve as versatile building blocks for a broad range of chemical and enzymatic reactions, resulting in highly valuable products for many applications Hydroxynitrile lyases comprise a diverse group of enzymes that catalyze the reversible cleavage of cyanohydrins to carbonyl compounds and hydrogen cyanide The enzymes have been studied broadly concerning their substrate scope, specificity, structure, and reaction mechanism, and many have been successfully applied and engineered for the synthesis of cyanohydrins from laboratory to industrial scale Both R-and S-cyanohydrins are accessible from a broad variety of substrates and, in most cases, high yields and enantiopurities can be obtained after enzyme and reaction engineering Recent progress in the development and optimization of heterologous expression systems make recombinant hydroxynitrile lyases available in the quantities needed for industrial production The procedures for safe handling of cyanides are also well-defined and established In addition, some hydroxynitrile lyases are able to catalyze the nonnatur-al asymmetric Henry reaction Although the enzyme activities are rather low, the enzymatic synthesis of enantiopure β-nitro alcohols shows promising results.

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-WeylMethoden 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 expert-evaluated 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.

Preface V

Volume Editors' Preface IX

Abstracts XIII

Table of Contents XXV

2.1 C—C Bond Formation 1

      2.1.1 Cyanohydrin Formation/Henry Reaction

      K Steiner, A Clieder, and M Gruber-Khadjawi 1

      2.1.2 Aldol Reactions

      P Clapes 31

      2.1.3 Acyloin, Benzoin, and Related Reactions

      M Pohl, C Wechsler, and M Mulier 93

      2.1.4 Enzymatic Carboxylation and Decarboxylation

      R Lewin, M L Thompson, and J Micklefield 133

      2.1.5 Addition to C=N Bonds

      A Ilari, A Bonamore, and A Boffi 159

2.2 Enzymatic C-Alkylation of Aromatic Compounds

L A Wessjohann, H F Schreckenbach, and C N Kaluderovic 177

2.3 Addition to C=C Bonds 213

      2.3.1 Addition of Hydrogen to C=C Bonds: Alkene Reduction

      K Faber and M Hall 213

      2.3.2 Addition of Water to C=C Bonds

      V Resch and U Hanefeld 261

      2.3.3 Addition of Ammonia and Amines to C=C Bonds

      S Bartsch and A Vogel 291

      2.3.4 Enzymatic Carbon—Carbon Bond-Forming Michael-Type Additions

      E M Geertsema and G J Poelarends 313

2.4 Transamination and Reductive Amination 335

      2.4.1 Amino Acid and Amine Dehydrogenases

      A S Bommarius and S K Au 335

      2.4.2 Imine Reductases

      F Leipold, S Hussain, S P France, and N J Turner 359

      2.4.3 co-Transaminases

      R C Simon, E Busto, E.-M Fischereder, C S Fuchs, D Pressnitz, N Richter,

      and W Kroutil 383

2.5 Carbonyl Reduction 421

      2.5.1 Ketone and Aldehyde Reduction

      T S Moody, S Mix, G Brown, and D Beecher 421

      2.5.2 Carboxylic Acid Reductase

      A S Lamm, P Venkitasubramanian, and J P N Rosazza 459

2.6 Epoxide Conversions 479

      2.6.1 Asymmetric Synthesis of Enantiopure Epoxides Using Monooxygenases

      A T Li and Z Li 479

      2.6.2 Reactions Catalyzed by Halohydrin Dehalogenases

      M Majeric Elenkov, W Szymahski, and D B Janssen 507

      2.6.3 Epoxide Hydrolysis

      R Wohlgemuth 529

Keyword Index 557

Author Index 591

Abbreviations 629

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