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 our understanding of the natural world increases, we begin to understand complex phenomena at molecular levels. This level of understanding allows for the design of molecular entities for functions ranging from material science to biology. Such design requires synthesis and, as the structures increase in complexity as a necessity for specificity, puts increasing demands on the level of sophistication of the synthetic methods. Such needs stimulate the improvement of existing methods and, more importantly, the development of new methods. As scientists confront the synthetic problems posed by the molecular targets, they require access to a source of reliable synthetic information. Thus, the need for a new, comprehensive, and critical treatment of synthetic chemistry has become apparent. To meet this challenge, an entirely new edition of the esteemed reference work Houben–Weyl Methods of Organic Chemistry will be published starting in the year 2000.

To reflect the new broader need and focus, this new edition has a new title, Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. Science of Synthesis will benefit from more than 90 years of experience and will continue the tradition of excellence in publishing synthetic chemistry reference works. Science of Synthesis will be a balanced and critical reference work produced by the collaborative efforts of chemists, from both industry and academia, selected by the editorial board. All published results from journals, books, and patent literature from the early 1800s until the year of publication will be considered by our authors, who are among the leading experts in their field. The 48 volumes of Science of Synthesis will provide chemists with the most reliable methods to solve their synthesis problems. Science of Synthesis will be updated periodically and will become a prime source of information for chemists in the 21st century.

Science of Synthesis will be organized in a logical hierarchical system based on the target molecule to be synthesized. The critical coverage of methods will be supported by information intended to help the user choose the most suitable method for their application, thus providing a strong foundation from which to develop a successful synthetic route. Within each category of product, illuminating background information such as history, nomenclature, structure, stability, reactivity, properties, safety, and environmental aspects will be discussed along with a detailed selection of reliable methods. Each method and variation will be accompanied by reaction schemes, tables of examples, experimental procedures, and a background discussion of the scope and limitations of the reaction described.

The policy of the editorial board is to make Science of Synthesis the ultimate tool for the synthetic chemist in the 21st century.

We would like to thank all of our authors for submitting contributions of such outstanding quality, and, also for the dedication and commitment they have shown throughout the entire editorial process.

October 2000

The Editorial Board

D. Bellus (Basel, Switzerland)

E. N. Jacobsen (Cambridge, USA)

S. V. Ley (Cambridge, UK)

R. Noyori (Nagoya, Japan)

M. Regitz (Kaiserslautern, Germany)

P. J. Reider (New Jersey, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

I. Shinkai (Tsukuba, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Volume Editor's Preface

The hydroxy group is arguably the fundamental functional group of organic chemistry, to which many reactions lead and from which many reactions flow. The hydroxy function is also ubiquitous in biology, being present in almost all major classes of biological molecules or their precursors. Alcohols are the products of many of the most important C—C bond forming reactions available to chemists, and this volume sets out to survey and present the best of the vast array of methods for making alcohols.

I would like to express my personal thanks to the many authors who have given their expertise, time, and commitment to allow this volume to be completed. I am indebted to Jim Thomas for his invitation to edit the volume, along with his assistance particularly in the planning and proofing stages. The editorial team of Fiona Shortt de Hernandez at Thieme have provided abundant support during the volume's development and I am particularly indebted to Toby Reeve for his valuable assistance during this time.

Manchester, November 2007

Volume Editor

Jonathan Clayden

Table of Contents

Introduction

J. Clayden

Introduction

36.1 Product Class 1: Alkanols

36.1.1 Synthesis by Oxidation

M. J. Porter

36.1.1 Synthesis by Oxidation

36.1.1.1 Method 1: Oxidation of Alkanes

36.1.1.1.1 Variation 1: Oxidation with Molecular Oxygen

36.1.1.1.2 Variation 2: Oxidation with Ozone

36.1.1.1.3 Variation 3: Oxidation with Dioxiranes

36.1.1.1.4 Variation 4: Oxidation with Oxaziridines

36.1.1.1.5 Variation 5: Oxidation with Peroxy Acids

36.1.1.1.6 Variation 6: Oxidation with Fluorine

36.1.1.1.7 Variation 7: Oxidation with Metal Porphyrins

36.1.1.1.8 Variation 8: Oxidation with Ruthenium Compounds

36.1.1.1.9 Variation 9: Oxidation with Chromium Compounds

36.1.1.1.10 Variation 10: Oxidation with Methyltrioxorhenium(VII)

36.1.1.1.11 Variation 11: Biocatalytic Oxidation

36.1.1.2 Method 2: Oxidation of Organosilicon Compounds

36.1.1.2.1 Variation 1: Oxidation of Trichlorosilanes

36.1.1.2.2 Variation 2: Oxidation of Alkoxysilanes with Hydrogen Peroxide

36.1.1.2.3 Variation 3: Oxidation of Alkoxysilanes with Peroxy Acids

36.1.1.2.4 Variation 4: Oxidation of Alkoxysilanes with Molecular Oxygen

36.1.1.2.5 Variation 5: Oxidation of Dimethyl(phenyl)silanes

36.1.1.3 Method 3: Oxidation of Organoboron Compounds

36.1.1.3.1 Variation 1: Oxidation with Basic Hydrogen Peroxide

36.1.1.3.2 Variation 2: Oxidation with Sodium Perborate and Sodium Percarbonate

36.1.1.3.3 Variation 3: Oxidation with Trimethylamine N-Oxide

36.1.1.4 Method 4: Oxidation of Organomercury Compounds

36.1.1.5 Method 5: Oxidation of Organolithium, Organomagnesium, Organozinc, and Organocopper Compounds

36.1.1.5.1 Variation 1: Oxidation with Molecular Oxygen

36.1.1.5.2 Variation 2: Oxidation with Alkyl Hydroperoxides

36.1.1.5.3 Variation 3: Oxidation with Bis(trimethylsilyl) Peroxide

36.1.1.5.4 Variation 4: Oxidation with Oxaziridines

36.1.2 Synthesis by Reduction

L. R. Cox

36.1.2 Synthesis by Reduction

36.1.2.1 Synthesis of Primary Aliphatic Alkanols

36.1.2.1.1 Method 1: Reduction of Carboxylic Acids

36.1.2.1.1.1 Variation 1: Using Metal Aluminum Hydrides and Alkoxyaluminum Hydrides 55

36.1.2.1.1.2 Variation 2: Using Metal Borohydrides and Related Compounds

36.1.2.1.1.3 Variation 3: Using Boranes and Related Compounds

36.1.2.1.1.4 Variation 4: Using Alane and Related Compounds

36.1.2.1.1.5 Variation 5: Using Samarium(II) Iodide

36.1.2.1.1.6 Variation 6: Transition-Metal-Catalyzed Reduction

36.1.2.1.1.7 Variation 7: Electrochemical Reduction

36.1.2.1.1.8 Variation 8: Enzymatic Reduction

36.1.2.1.1.9 Variation 9: By In Situ Derivatization

36.1.2.1.2 Method 2: Reduction of Esters

36.1.2.1.2.1 Variation 1: Using Metal Aluminum Hydrides and Related Systems

36.1.2.1.2.2 Variation 2: Using Metal Borohydrides and Related Systems

36.1.2.1.2.3 Variation 3: Using Boranes

36.1.2.1.2.4 Variation 4: Using Alane and Other Neutral Organoaluminum Reagents

36.1.2.1.2.5 Variation 5: Using Silanes and Siloxanes

36.1.2.1.2.6 Variation 6: Using Dissolving Metal Conditions

36.1.2.1.2.7 Variation 7: Using Samarium(II) Iodide

36.1.2.1.2.8 Variation 8: Transition-Metal-Catalyzed Hydrogenation

36.1.2.1.2.9 Variation 9: Electrochemical Reduction

36.1.2.1.3 Method 3: Reduction of Amides

36.1.2.1.3.1 Variation 1: Using Aluminum Hydrides and Borohydride Reducing Agents

36.1.2.1.3.2 Variation 2: Using Boranes

36.1.2.1.3.3 Variation 3: Using Dissolving Metals

36.1.2.1.3.4 Variation 4: Using Samarium(II) Iodide

36.1.2.1.3.5 Variation 5: Electrochemical Reduction

36.1.2.1.3.6 Variation 6: Transition-Metal-Catalyzed Hydrogenation

36.1.2.1.4 Method 4: Reduction of Acid Halides and Acid Anhydrides

36.1.2.1.4.1 Variation 1: Using Aluminum Hydride and Alkoxyaluminum Hydride Reducing Agents

36.1.2.1.4.2 Variation 2: Using Borohydride Reducing Agents

36.1.2.1.4.3 Variation 3: Using Boranes or Alane and Related Reagents

36.1.2.1.4.4 Variations 4: Miscellaneous Reductions

36.1.2.1.5 Method 5: Reduction of Thioesters

36.1.2.1.5.1 Variation 1: Using Aluminum Hydrides

36.1.2.1.5.2 Variation 2: Using Borohydrides

36.1.2.1.5.3 Variation 3: Using Neutral Organoaluminum Reagents

36.1.2.1.5.4 Variation 4: Using Heterogeneous Nickel Catalysts

36.1.2.1.6 Method 6: Reduction of Nitriles

36.1.2.1.6.1 Variation 1: Reactions Proceeding via the Intermediate Aldehyde

36.1.2.1.6.2 Variation 2: Reactions Proceeding via the Intermediate Carboxylic Acid or Ester

36.1.2.1.7 Method 7: Reduction of Aldehydes

36.1.2.1.7.1 Variation 1: Using Metal Borohydrides

36.1.2.1.7.2 Variation 2: Using Aluminum Hydrides and Related Reagents

36.1.2.1.7.3 Variation 3: Using Borane, Alane, and Related Systems

36.1.2.1.7.4 Variation 4: Using Organosilanes and Related Systems

36.1.2.1.7.5 Variation 5: Using Organostannanes and Organostibines

36.1.2.1.7.6 Variation 6: Using Alkali Metal and Alkaline Earth Metal Hydrides and Related Systems

36.1.2.1.7.7 Variation 7: Using Meerwein–Ponndorf–Verley-Type Reactions

36.1.2.1.7.8 Variation 8: Transition-Metal-Catalyzed Reduction: Hydrogenation and Transfer Hydrogenation

36.1.2.1.7.9 Variation 9: Using Single-Electron-Transfer Reduction Strategies

36.1.2.1.7.10 Variations 10: Miscellaneous Strategies

36.1.2.1.8 Method 8: Reductive Ring Opening of Cyclic Ethers

36.1.2.1.8.1 Variation 1: Using Borohydrides and Aluminum Hydrides

36.1.2.1.8.2 Variation 2: Using Boranes and Neutral Aluminum Hydride Reagents

36.1.2.1.8.3 Variation 3: Using Silanes

36.1.2.1.8.4 Variation 4: Transition-Metal-Catalyzed Hydrogenolysis of Cyclic Ethers

36.1.2.1.8.5 Variation 5: Using Single-Electron-Transfer Agents

36.1.2.1.9 Method 9: Reduction of Peroxides and Related Systems

36.1.2.1.9.1 Variation 1: Reduction of Hydroperoxides and Peroxides

36.1.2.1.9.2 Variation 2: Reduction of Ozonides

36.1.2.1.9.3 Variation 3: Reduction of Hydroxylamines

36.1.2.2 Synthesis of Secondary Aliphatic Alkanols

36.1.2.2.1 Method 1: Reduction of Ketones

36.1.2.2.1.1 Variation 1: Using Metal Aluminum Hydrides and Related Systems

36.1.2.2.1.2 Variation 2: Using Borohydride Reducing Agents and Related Systems

36.1.2.2.1.3 Variation 3: Using Boranes and Related Systems

36.1.2.2.1.4 Variation 4: Using Silanes and Related Systems

36.1.2.2.1.5 Variation 5: Using Stannanes and Related Systems

36.1.2.2.1.6 Variation 6: Using Alkali Metal and Alkaline Earth Metal Hydrides and Related Systems

36.1.2.2.1.7 Variation 7: Using Meerwein–Ponndorf–Verley-Type Reactions

36.1.2.2.1.8 Variation 8: Transition-Metal-Catalyzed Hydrogenation and Transfer Hydrogenation

36.1.2.2.1.9 Variation 9: Using Single-Electron-Transfer Methods

36.1.2.2.1.10 Variation 10: Electrochemical Reduction

36.1.2.2.1.11 Variations 11: Miscellaneous Procedures

36.1.2.2.2 Method 2: Enantioselective Reduction of Ketones

36.1.2.2.2.1 Variation 1: Asymmetric Transition-Metal-Catalyzed Hydrogenation and Transfer Hydrogenation

36.1.2.2.2.2 Variation 2: Biocatalytic Reduction Methods

36.1.2.2.3 Method 3: Reductive Ring Opening of Cyclic Ethers

36.1.2.2.3.1 Variation 1: Using Metal Aluminum Hydrides

36.1.2.2.3.2 Variation 2: Using Metal Borohydrides and Related Reagents

36.1.2.2.3.3 Variation 3: Using Boranes, Alanes, and Related Reagents

36.1.2.2.3.4 Variation 4: Transition-Metal-Catalyzed Hydrogenolysis of Cyclic Ethers

36.1.2.2.3.5 Variation 5: Using Single-Electron-Transfer Methods

36.1.2.2.3.6 Variation 6: Lewis Acid Mediated Silane Reduction of Cyclic Ethers

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