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 48: Alkanes

Preface

Table of Contents

Introduction

H. Hiemstra

48.1 Product Class 1: Acyclic Alkanes

48.1.1 Synthesis by Metal Substitution with Retention of the Carbon Framework

E. A. B. Kantchev and M. G. Organ

48.1.2 Synthesis by Metal Substitution with Extension of the Carbon Framework

E. A. B. Kantchev and M. G. Organ

48.1.3 Synthesis by Reduction without C-C Bond Cleavage

48.1.3.1 Reduction of Carbonic or Carboxylic Acids, Aldehydes, Ketones, or Derivatives

J. Wicha

48.1.3.2 Reduction of Haloalkanes

P. Margaretha

48.1.3.3 Reduction of Alkanols and Derivatives

J. Wicha

48.1.3.4 Reduction of Other Heterofunctionalities

J. Drabowicz, D. Krasowska, and J. Wicha

48.1.3.5 Reduction of Alkynes

N. Chessum, S. Couty, and K. Jones

48.1.3.6 Reduction of Alkenes

48.1.3.6.1 Reduction by Heterogeneous Catalysis

N. Chessum, S. Couty, and K. Jones

48.1.3.6.2 Reduction by Homogeneous Catalysis or Biocatalysis

M. Tsukamoto and M. Kitamura

48.1.3.6.3 Reduction by Noncatalytic Methods

M. Zaidlewicz, M. P. Krzemiński, and A. Dzieleńdziak

48.1.4 Synthesis by Reduction of Alkenes via Intermolecular C-C Bond Formation

P. Eilbracht

48.1.5 Synthesis by Reduction with C-C Bond Cleavage

P. Margaretha

48.1.6 Synthesis from Other Alkanes

48.1.6.1 Bond Cleavage Reactions

Á. Molnár and P. Margaretha

48.1.6.2 Dehydrodimerization Reactions

Á Molnár

48.1.6.3 Isomerization Reactions

ÁMolnár

48.2 Product Class 2: Cyclopropanes

A. de Meijere and S. I. Kozhushkov

48.3 Product Class 3: Cyclobutanes

R. Kostikov and M. S. Baird

48.4 Product Class 4: Five-Membered and Larger-Ring Cycloalkanes

M. J. Palframan and A. F. Parsons

48.5 Product Class 5: Hydrocarbon Polymers

W. Kaminsky

Keyword Index

Author Index

Abbreviations

Table of Contents

Introduction

H. Hiemstra

Introduction

48.1 Product Class 1: Acyclic Alkanes

48.1.1 Synthesis by Metal Substitution with Retention of the Carbon Framework

E. A. B. Kantchev and M. G. Organ

48.1.1 Synthesis by Metal Substitution with Retention of the Carbon Framework

48.1.1.1 Method 1: Synthesis by Protonation of Carbon-Metal Bonds

48.1.1.1.1 Variation 1: Acidolysis of Alkyl Derivatives of Metals from Groups 14 and 15 (Including Boron)

48.1.1.1.2 Variation 2: Protonolysis of Alkyl Derivatives of Metals from Groups 5–11

48.1.1.1.3 Variation 3: Protonolysis of Alkyl Derivatives of Metals from Groups 3, 4, 12, and 13 (Including Lanthanides and Actinides, Excluding Boron)

48.1.1.1.4 Variation 4: Protonolysis of Alkyl Derivatives of Metals from Groups 1 and 2

48.1.1.2 Method 2: Synthesis by Hydrogenolysis of Carbon-Metal Bonds

48.1.1.2.1 Variation 1: Hydrogenolysis and Reductive Cleavage of Carbon—Metal Bonds

48.1.1.2.2 Variation 2: Reductive Elimination from Alkyl–Transition Metal Hydrido Complexes

48.1.2 Synthesis by Metal Substitution with Extension of the Carbon Framework

E. A. B. Kantchev and M. G. Organ

48.1.2 Synthesis by Metal Substitution with Extension of the Carbon Framework

48.1.2.1 Method 1: Noncatalyzed Coupling Reactions of Nonactivated Alkyl Electrophiles with Organometallic Reagents

48.1.2.1.1 Variation 1: Using Main-Group Organometallic Reagents

48.1.2.1.2 Variation 2: Using Transition-Metal Organometallic Reagents

48.1.2.2 Method 2: Catalyzed Coupling Reactions of Nonactivated Alkyl Electrophiles with Organometallic Reagents

48.1.2.2.1 Variation 1: Couplings of Alkyl Grignard Reagents (Kumada–Tamao–Corriu Reaction) Mediated by Copper, Silver, Nickel, Palladium, Iron, and Cobalt

48.1.2.2.2 Variation 2: Couplings of Alkylzinc Reagents (Negishi Reaction) Mediated by Nickel and Palladium

48.1.2.2.3 Variation 3: Couplings of Alkyl Boron Compounds (Suzuki–Miyaura Reaction) Mediated by Palladium and Nickel

48.1.2.2.4 Variation 4: Couplings of Other Alkyl Organometallic Compounds

48.1.2.3 Method 3: Oxidative Coupling of Alkyl Organometallic Reagents

48.1.2.3.1 Variation 1: Reductive Elimination from Dialkyl Transition-Metal Complexes

48.1.2.3.2 Variation 2: Kolbe Electrolysis

48.1.2.4 Method 4: Reductive Coupling of Alkyl Halides

48.1.3 Synthesis by Reduction without C-C Bond Cleavage

48.1.3.1 Reduction of Carbonic or Carboxylic Acids, Aldehydes, Ketones, or Derivatives

J. Wicha

48.1.3.1 Reduction of Carbonic or Carboxylic Acids, Aldehydes, Ketones, or Derivatives

48.1.3.1.1 Method 1: The Clemmensen Reduction (Deoxygenation of Aldehydes or Ketones Using Zinc and Hydrochloric Acid)

48.1.3.1.1.1 Variation 1: Reduction with Zinc–Hydrochloric Acid in an Aqueous Solution

48.1.3.1.1.2 Variation 2: Reduction with Zinc–Hydrochloric Acid in the Presence of Water-Miscible Solvents

48.1.3.1.1.3 Variation 3: Reduction with Zinc–Hydrochloric Acid in the Presence of Water-Immiscible Solvents

48.1.3.1.1.4 Variation 4: Reduction with Zinc in Organic Solvents Saturated with Hydrogen Chloride

48.1.3.1.1.5 Variation 5: Ultrasound-Assisted Zinc–Protic Acid Reduction

48.1.3.1.1.6 Variation 6: Miscellaneous Methods

48.1.3.1.2 Method 2: Other Direct Deoxygenation Methods

48.1.3.1.2.1 Variation 1: Deoxygenation of Aromatic Ketones with Hydrogen Iodide

48.1.3.1.2.2 Variation 2: Deoxygenation of Carbonyl Compounds by Catalytic Hydrogenation

48.1.3.1.2.3 Variation 3: Deoxygenation of Aromatic Acids, Aldehydes, and Ketones Using the Trichlorosilane–Tripropylamine Couple

48.1.3.1.2.4 Variation 4: Deoxygenation of Ketones Using the Triethylsilane–Trifluoroacetic Acid Couple

48.1.3.1.2.5 Variation 5: Deoxygenation of Carboxylic Acids, Esters, Aldehydes, and Ketones Using Silanes in the Presence of Lewis Acids

48.1.3.1.2.6 Variation 6: Deoxygenation of Aromatic and Æ, -Unsaturated Ketones Using the Sodium Borohydride–Trifluoroacetic Acid Couple

48.1.3.1.2.7 Variation 7: Miscellaneous Methods

48.1.3.1.3 Method 3: The Wolff–Kishner Reduction (Reduction of Aldehydes and Ketones via Hydrazones)

48.1.3.1.3.1 Variation 1: The Huang-Minlon Modification

48.1.3.1.3.2 Variation 2: The Barton Modification

48.1.3.1.3.3 Variation 3: The Cram and the Henbest Modifications

48.1.3.1.3.4 Variation 4: The Nagata–Itazaki Modification

48.1.3.1.3.5 Variation 5: The Furrow–Myers Modification

48.1.3.1.3.6 Variation 6: Microwave-Assisted Wolff–Kishner Reductions

48.1.3.1.3.7 Variation 7: Miscellaneous Reactions

48.1.3.1.4 Method 4: Reduction of Aldehydes and Ketones via Tosylhydrazones

48.1.3.1.4.1 Variation 1: Reduction of Tosylhydrazones with Lithium Aluminum Hydride

48.1.3.1.4.2 Variation 2: Reduction of Tosylhydrazones with Sodium Borohydride

48.1.3.1.4.3 Variation 3: Reduction of Tosylhydrazones with Sodium Cyanoborohydride–Protic Acid

48.1.3.1.4.4 Variation 4: Reduction of Tosylhydrazones with Catecholborane

48.1.3.1.4.5 Variation 5: Miscellaneous Methods

48.1.3.1.5 Method 5: Deoxygenation of Aldehydes and Ketones via Dithioacetals and Other Sulfur-Containing Derivatives

48.1.3.1.5.1 Variation 1: Reduction of Dithioacetals Using Raney Nickel

48.1.3.1.5.2 Variation 2: Reduction of Dithioacetals Using Dissolving Metals

48.1.3.1.5.3 Variation 3: Reduction of Dithioacetals Using Tributyltin Hydride

48.1.3.1.5.4 Variation 4: Reduction of Dithioacetals with Hydrazine

48.1.3.1.5.5 Variation 5: Miscellaneous Methods

48.1.3.2 Reduction of Haloalkanes

P. Margaretha

48.1.3.2 Reduction of Haloalkanes

48.1.3.2.1 Method 1: Alkanes from Fluoroalkanes

48.1.3.2.1.1 Variation 1: Reduction of Fluoroalkanes with Alkali Metals

48.1.3.2.1.2 Variation 2: Reduction of Fluoroalkanes with Hydrides

48.1.3.2.2 Method 2: Alkanes from Chloroalkanes

48.1.3.2.2.1 Variation 1: Reductive Cleavage of Chloroalkanes

48.1.3.2.2.2 Variation 2: Reductive Cleavage of Bromochloroalkanes

48.1.3.2.3 Method 3: Alkanes from Bromoalkanes

48.1.3.2.3.1 Variation 1: Reductive Cleavage of Bromoalkanes

48.1.3.2.4 Method 4: Alkanes from Iodoalkanes

48.1.3.3 Reduction of Alkanols and Derivatives

J. Wicha

48.1.3.3 Reduction of Alkanols and Derivatives

48.1.3.3.1 Method 1: Direct Replacement of C-OH Bonds by C-H Bonds in Benzylic, Allylic, or Other Activated Alcohols

48.1.3.3.1.1 Variation 1: Acid-Promoted Catalytic Hydrogenolysis of Alcohols

48.1.3.3.1.2 Variation 2: Dissolving-Metal Reduction of Benzylic Alcohols

48.1.3.3.1.3 Variation 3: Reduction of Alcohols by Mixed Metal Hydrides in the Presence of Lewis or Protic Acids

48.1.3.3.1.4 Variation 4: Reduction of Alcohols with the Triethylsilane/Trifluoroacetic Acid System or Other Silane/Acid Combinations

48.1.3.3.1.5 Variation 5: Deoxygenation of Alcohols with Diiododimethylsilane or Iodotrimethylsilane

48.1.3.3.1.6 Variation 6: Microwave-Promoted Deoxygenation of Benzylic Alcohols with Lawesson s Reagent and Hexacarbonylmolydenum(0) Catalyst

48.1.3.3.1.7 Variation 7: Deoxygenation of Alcohols by Electrolysis in the Presence of a Trialkyl- or Triarylphosphine

48.1.3.3.1.8 Variation 8: Deoxygenation of Æ-Hydroxy Ketones or Æ-Hydroxyaldehydes

48.1.3.3.1.9 Variation 9: Deoxygenation of Alcohols via Diazenes

48.1.3.3.2 Method 2: Deoxygenation of Alcohols via Carboxylic Esters

48.1.3.3.2.1 Variation 1: Photolysis of Carboxylic Esters

48.1.3.3.2.2 Variation 2: Deoxygenation of Alcohols through Electrochemical Reduction of Their Esters

48.1.3.3.2.3 Variation 3: Dissolving-Metal Deoxygenation of Alcohols via Their Carboxylic Esters

48.1.3.3.2.4 Variation 4: Deoxygenation of Alcohols via Their N,N¢-Dicyclohexylcarbamimidate Esters

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