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 38: Peroxides

Preface

Table of Contents

Introduction

A. Berkessel

38.1 Product Class 1: Alkyl and Cycloalkyl Hydroperoxides

A. Scarso and G. Strukul

38.2 Product Class 2: Allylic Hydroperoxides

U. Bergsträßer and J. Hartung

38.3 Product Class 3: Benzylic Hydroperoxides

J. Hartung and H. Heydt

38.4 Product Class 4: Salts of Alkyl Hydroperoxides

A. Scarso and G. Strukul

38.5 Product Class 5: Alkyl and Cycloalkyl Peroxides

G. Vassilikogiannakis and T. Montagnon

38.6 Product Class 6: Allylic Peroxides

I. N. Lykakis and M. Stratakis

38.7 Product Class 7: Benzylic Peroxides

M. R. Iesce and M. DellaGreca

38.8 Product Class 8: Monocyclic Peroxides

38.8.1 Product Subclass 1: Three-Membered Cyclic Peroxides (Dioxiranes)

B. Wang and Y. Shi

38.8.2 Product Subclass 2: Four-Membered Cyclic Peroxides (1,2-Dioxetanes and 1,2-Dioxetanones)

W. J. Baader and E. L. Bastos

38.8.3 Product Subclass 3: Five-Membered Cyclic Peroxides with No Further Heteroatoms in the Ring (1,2-Dioxolanes and 1,2-Dioxolan-3-ones)

W. J. Baader and E. L. Bastos

38.8.4 Product Subclass 4: Five-Membered Cyclic Peroxides with One Further Oxygen Atom in the Ring (1,2,4-Trioxolanes)

W. J. Baader and E. L. Bastos

38.8.5 Product Subclass 5: Six-Membered Cyclic Peroxides with No Further Heteroatoms in the Ring (1,2-Dioxanes and 3,6-Dihydro-1,2-dioxins)

W. J. Baader and E. L. Bastos

38.8.6 Product Subclass 6: Six-Membered Cyclic Peroxides with One Further Oxygen Atom in the Ring (1,2,4-Trioxanes)

W. J. Baader and E. L. Bastos

38.8.7 Product Subclass 7: Six-Membered Cyclic Peroxides with Two Further Oxygen Atoms in the Ring (1,2,4,5-Tetroxanes)

W. J. Baader and E. L. Bastos

38.9 Product Class 9: Larger-Ring Cyclic Peroxides and Endoperoxides

M. N. Alberti, M. D. Tzirakis, and M. Orfanopoulos

Keyword Index

Author Index

Abbreviations

Table of Contents

Introduction

A. Berkessel

Introduction

38.1 Product Class 1: Alkyl and Cycloalkyl Hydroperoxides

A. Scarso and G. Strukul

38.1 Product Class 1: Alkyl and Cycloalkyl Hydroperoxides

38.1.1 Product Subclass 1: α-Unsubstituted Alkyl Hydroperoxides

38.1.1.1 Synthesis of Product Subclass 1

38.1.1.1.1 Method 1: Reactions of Alkanes with Molecular Oxygen

38.1.1.1.2 Method 2: Hydrolysis of Alkyl Metal and Alkyl Metalloid Peroxides

38.1.1.1.2.1 Variation 1: Via Oxidation of Alkylmagnesium Halides with Molecular Oxygen

38.1.1.1.2.2 Variation 2: Via Oxidation of Alkylboron Halides with Molecular Oxygen

38.1.1.1.3 Method 3: Reaction of Oxetanes with Hydrogen Peroxide

38.1.1.1.4 Method 4: Reaction of Epoxides with Hydrogen Peroxide

38.1.1.1.4.1 Variation 1: Catalyzed by Methyltrioctylammonium Tetrakis(oxodiperoxotungsto)phosphate

38.1.1.1.5 Method 5: Reaction of Alkyl Halides

38.1.1.1.5.1 Variation 1: With Hydrogen Peroxide in the Presence of Silver(I) Trifluoroacetate

38.1.1.1.5.2 Variation 2: With 2-Alkoxypropan-2-yl and 2-(2-Methoxyethoxy)propan-2-yl Hydroperoxides

38.1.1.1.5.3 Variation 3: With Potassium Superoxide

38.1.1.1.6 Method 6: Reaction of Alcohols with Hydrogen Peroxide

38.1.1.1.6.1 Variation 1: Without Catalysts

38.1.1.1.6.2 Variation 2: With Acid Catalysis

38.1.1.1.7 Method 7: Reaction of Dialkyl Sulfates with Hydrogen Peroxide

38.1.1.1.8 Method 8: Reaction of Alkyl Methanesulfonates with Hydrogen Peroxide

38.1.1.1.8.1 Variation 1: Reaction of Homoallylic Methanesulfonates with Hydrogen Peroxide

38.1.1.1.8.2 Variation 2: Reaction of Cyclic Homoallylic 4-Bromobenzenesulfonates with Hydrogen Peroxide

38.1.1.1.9 Method 9: Reaction of 1-Substituted 1-Sulfonylhydrazines with Molecular Oxygen under Basic Conditions

38.1.1.1.10 Method 10: Reaction of 1-Alkyl-2-tosylhydrazines with Hydrogen Peroxide and Sodium Peroxide

38.1.1.1.11 Method 11: Synthesis from Alkenes

38.1.1.1.11.1 Variation 1: With Triethylsilane and Oxygen with a Cobalt(II) Catalyst

38.1.1.1.11.2 Variation 2: Photooxygenation with Methylene Blue Sensitizer

38.1.1.1.11.3 Variation 3: Photooxygenation with 4-Chlorobenzenethiol

38.1.1.1.11.4 Variation 4: With N-Bromosuccinimide and Hydrogen Peroxide

38.1.1.1.11.5 Variation 5: With 1,3-Dibromo-5,5-dimethylhydantoin and Hydrogen Peroxide

38.1.1.1.12 Method 12: Synthesis from Conjugated Dienes

38.1.1.1.13 Method 13: Synthesis from Peroxy Esters

38.1.1.2 Applications of Product Subclass 1 in Organic Synthesis

38.1.2 Product Subclass 2: α-Halogen-Substituted Alkyl Hydroperoxides

38.1.2.1 Synthesis of Product Subclass 2

38.1.2.1.1 α-Fluoroalkyl Hydroperoxides

38.1.2.1.1.1 Method 1: Decomposition of Hexafluoroacetone Perhydrate

38.1.2.1.1.2 Method 2: Reaction of Perfluoroperoxy Derivatives with Water

38.1.2.1.2 α-Chloroalkyl Hydroperoxides

38.1.2.1.2.1 Method 1: Reaction of Chloroalkenes with Ozone

38.1.3 Product Subclass 3: α-Oxygen-Substituted Alkyl Hydroperoxides

38.1.3.1 Synthesis of Product Subclass 3

38.1.3.1.1 α-Hydroxyalkyl Hydroperoxides

38.1.3.1.1.1 Method 1: Reaction of Aldehydes with Hydrogen Peroxide and Iodine

38.1.3.1.1.2 Method 2: Reaction of α-Halo Ketones with Hydrogen Peroxide

38.1.3.1.2 α-Alkoxyalkyl Hydroperoxides

38.1.3.1.2.1 Method 1: Ozonolysis of Alkenes

38.1.3.1.2.2 Method 2: Reaction of Vinyl Ethers with Ozone and Alcohols

38.1.3.1.2.2.1 Variation 1: With Hydrogen Peroxide

38.1.3.1.2.2.2 Variation 2: With Hydrogen Peroxide and Silica Gel

38.1.3.1.2.2.3 Variation 3: With Hydrogen Peroxide and Molybdenum(VI) Oxide

38.1.3.1.2.3 Method 3: Reaction of Dialkyl Ethers with Molecular Oxygen

38.1.3.1.2.4 Method 4: α-Reaction of Cyclopropyl Alcohols with Hydrogen Peroxide

38.1.3.1.2.5 Method 5: Reaction of Ketones and Alcohols with Hydrogen Peroxide

38.1.3.1.2.6 Method 6: Reaction of Hydroxy Ketones and Diketones with Hydrogen Peroxide

38.1.3.1.2.7 Method 7: Reaction of Ketones with Hydrogen Peroxide Catalyzed by Iodine

38.1.3.1.2.8 Method 8: Reaction of Homoallylic 4-Bromobenzenesulfonates and Hydrogen Peroxide

38.1.3.1.2.9 Method 9: Ring Opening of Oxetanes with Hydrogen Peroxide

38.1.3.1.3 α-Peroxyalkyl Hydroperoxides

38.1.3.1.3.1 Method 1: Reaction of Alkenes and Vinyl Ethers with Ozone

38.1.3.1.3.1.1 Variation 1: Intramolecular Reaction of Alkyl Hydroperoxides with Carbonyl Oxides Generated by Ozonolysis of Alkenes

38.1.3.1.3.2 Method 2: Reaction of Ketones with Hydrogen Peroxide

38.1.3.1.3.3 Method 3: Reaction of Acetals with Hydrogen Peroxide Mediated by Boron Trifluoride–Diethyl Ether Complex

38.1.3.1.3.4 Method 4: Reaction of Dialkyl Ethers with Molecular Oxygen

38.1.3.1.4 α-(Triorganosiloxy)alkyl Hydroperoxides

38.1.3.1.4.1 Method 1: Reaction of Trialkylsilyl Vinyl Ethers and Hydrogen Peroxide

38.1.3.1.5 α-(Acyloxy)alkyl Hydroperoxides

38.1.3.1.5.1 Method 1: Photooxidation of an Enol Lactone

38.1.3.1.6 1,1-Bis(hydroperoxy)alkanes

38.1.3.1.6.1 Method 1: Reaction of Ketones with Hydrogen Peroxide with Acid Catalysts

38.1.3.1.6.1.1 Variation 1: With 1,2-Bis(diphenylphosphoryl)ethane

38.1.3.1.6.1.2 Variation 2: Catalyzed by Ammonium Cerium(IV) Nitrate

38.1.3.1.6.1.3 Variation 3: Catalyzed by Methyltrioxorhenium(VII) in Trifluoroethanol

38.1.3.1.6.1.4 Variation 4: Catalyzed by Molecular Iodine

38.1.3.1.6.1.5 Variation 5: Catalyzed by Tungstic Acid

38.1.3.1.6.2 Method 2: Reaction of Tosylhydrazones with Hydrogen Peroxide

38.1.3.1.6.3 Method 3: Reaction of Vinyl Ethers with Ozone and Hydrogen Peroxide

38.1.3.1.6.4 Method 4: Reaction of Ketals with Hydrogen Peroxide

38.1.3.1.6.5 Method 5: Ring Opening of Bicyclic Benzyl Alcohols with Hydrogen Peroxide

38.1.3.2 Applications of Product Subclass 3 in Organic Synthesis

38.1.4 Product Subclass 4: α-Sulfur-Substituted Alkyl Hydroperoxides

38.1.4.1 Synthesis of Product Subclass 4

38.1.4.1.1 Method 1: Photooxidation of Thiazolidines with Molecular Oxygen in the Presence of Tetraphenylphorphyrin

38.1.5 Product Subclass 5: α-Nitrogen-Substituted Alkyl Hydroperoxides

38.1.5.1 Synthesis of Product Subclass 5

38.1.5.1.1 α-Aminoalkyl Hydroperoxides

38.1.5.1.1.1 Method 1: Reaction of Carbonyl Compounds with Ammonia or Amines and Hydrogen Peroxide

38.1.5.1.2 α-(Acylamino)alkyl Hydroperoxides

38.1.5.1.2.1 Method 1: Reaction of Cyclic Amides and N-Alkylamides with Oxygen

38.1.5.1.2.2 Method 2: Reaction of N-Heterocycles with Hydrogen Peroxide

38.1.5.1.3 α-Hydrazinoalkyl Hydroperoxides

38.1.5.1.3.1 Method 1: Oxidation of Hydrazoalkanes

38.1.5.1.4 α-(N-Alkyl-N-nitrosoamino)alkyl Hydroperoxides

38.1.5.1.4.1 Method 1: Reaction of Dialkylnitrosamines with Lithium Diisopropylamide and Oxygen

38.1.5.1.4.2 Method 2: Reaction of 1-Acetoxyalkyl(alkyl)nitrosamines with Hydrogen Peroxide

38.1.5.1.5 4-Hydroperoxy-1,3,2-oxazaphosphorinane 2-Oxides

38.1.5.1.5.1 Method 1: Reaction of 4-Hydroxy-1,3,2-oxazaphosphorinane 2-Oxides with Hydrogen Peroxide

38.1.5.1.5.2 Method 2: Reaction of a Phosphoric Amide Diester Bearing O- or N-Alkenyl Residues and Ozone

38.1.5.2 Applications of Product Subclass 5 in Organic Synthesis

38.2 Product Class 2: Allylic Hydroperoxides

U. Bergsträßer and J. Hartung

38.2 Product Class 2: Allylic Hydroperoxides

38.2.1 Synthesis of Product Class 2

38.2.1.1 Method 1: Synthesis from Alkenes

38.2.1.1.1 Variation 1: With Triplet Dioxygen

38.2.1.1.2 Variation 2: With Singlet Dioxygen

38.2.1.2 Method 2: Synthesis from Arenes

38.2.1.2.1 Variation 1: Reaction with Dioxygen under Basic Conditions

38.2.1.2.2 Variation 2: Reaction with Triplet Dioxygen in the Presence of Transition Metal Compounds

38.2.1.2.3 Variation 3: Reaction with Singlet Dioxygen

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