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.

The Editorial Board                                                                                   October 2000

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 30: Acetals: O/N, S/S, S/N, and N/N and Higher Heteroatom Analogues

Preface

Table of Contents

Introduction

J. Otera

30.1 Product Class 1: O,N-Acetals

30.1.1 Product Subclass 1: Acyclic O,N-Acetals

C. Kibayashi and N. Yamazaki

30.1.2 Product Subclass 2: Cyclic O,N-Acetals

C. Kibayashi and N. Yamazaki

30.1.3 Product Subclass 3: Carbohydrate Derivatives (Including Nucleosides)

H. Yamada

30.2 Product Class 2: O,P- and S,P-Acetals

M. Yamashita

30.3 Product Class 3: S,S-Acetals

T.-Y. Luh and M.-k. Leung

30.3.1 Product Subclass 1: Acyclic S,S-Acetals

T. Takeda and A. Tsubouchi

30.3.2 Product Subclass 2:1,3-Dithietanes

T.-Y. Luh and M.-k. Leung

30.3.3 Product Subclass 3:1,3-Dithiolanes

M.-k. Leung and T.-Y. Luh

30.3.4 Product Subclass 4:1,3-Dithianes

M. Nakata

30.3.5 Product Subclass 5:1,3-Dithiepanes

M. Nakata

30.3.6 Product Subclass 6: Acyclic and Cyclic S,S-Acetal S-Oxides and S,S-Dioxides

K. Ogura

30.3.7 Deprotection of S,S-Acetals

H. Firouzabadi and N. Iranpoor

30.4 Product Class 4: S,N-Acetals (α-Amino Sulfur Derivatives)

C. Kibayashi and N. Yamazaki

30.5 Product Class 5: Selenium- and Tellurium-Containing Acetals

T. Murai and M. Yoshimatsu

30.6 Product Class 6: N,N-Acetals

C. Kibayashi and N. Yamazaki

30.7 Product Class 7: N,P- and P,P-Acetals

M. Yamashita

Keyword Index

Author Index

Abbreviations

Table of Contents

Introduction

J. Otera

Introduction

30.1 Product Class 1: O,N-Acetals

30.1.1 Product Subclass 1: Acyclic O,N-Acetals

C. Kibayashi and N. Yamazaki

30.1.1 Product Subclass 1: Acyclic O,N-Acetals

30.1.1.1 Synthesis of Product Subclass 1

30.1.1.1.1 Method 1: Addition to Imine Bonds

30.1.1.1.2 Method 2: Addition to Carbonyl Bonds

30.1.1.1.2.1 Variation 1: Addition of Amines to Carbonyl Bonds

30.1.1.1.2.2 Variation 2: Addition of Carbanions to Carbonyl Bonds

30.1.1.1.2.3 Variation 3: Addition of Hydrides to Carbonyl Bonds

30.1.1.1.3 Method 3: Transacetalization Reactions

30.1.1.1.4 Methods 4: Miscellaneous Syntheses

30.1.1.2 Applications of Product Subclass 1 in Organic Synthesis

30.1.1.2.1 Method 1: Preparation of Acyclic Compounds via C—C Bond Formation with Cleavage of a C—O Bond

30.1.1.2.2 Method 2: Preparation of Cyclic Compounds via C—C Bond Formation with Cleavage of a C—O Bond

30.1.1.2.3 Methods 3: Miscellaneous Transformations

30.1.2 Product Subclass 2: Cyclic O,N-Acetals

C. Kibayashi and N. Yamazaki

30.1.2 Product Subclass 2: Cyclic O,N-Acetals

30.1.2.1 Synthesis of Product Subclass 2

30.1.2.1.1 Method 1: Addition to Imine Bonds

30.1.2.1.2 Method 2: Addition to Carbonyl Bonds

30.1.2.1.2.1 Variation 1: Addition of Hydrides to Carbonyl Bonds

30.1.2.1.2.2 Variation 2: Addition of Amines to Carbonyl Bonds

30.1.2.1.2.3 Variation 3: Addition of Silirane to Carbonyl Bonds

30.1.2.1.3 Method 3: O,N-Acetalization of Carbonyl Compounds

30.1.2.1.3.1 Variation 1: Acetalization of Carbonyl Compounds with 8-Aminomenthol

30.1.2.1.3.2 Variation 2: Acetalization of Carbonyl Compounds with (S)-Proline

30.1.2.1.3.3 Variation 3: Acetalization of Carbonyl Compounds with (Hydroxymethyl)pyrrolidinone

30.1.2.1.3.4 Variation 4: Acetalization of Carbonyl Compounds with N-Mesylalanine

30.1.2.1.3.5 Variation 5: Acetalization of Carbonyl Compounds with Phenylglycinol

30.1.2.1.3.6 Variation 6: Acetalization of Carbonyl Compounds with Aminophenols

30.1.2.1.4 Method 4: Preparation of O,N-Acetals via Transacetalization

30.1.2.1.4.1 Variation 1: Via Intermolecular Transacetalization

30.1.2.1.4.2 Variation 2: Via Intramolecular Transacetalization

30.1.2.1.5 Methods 5: Miscellaneous Methods

30.1.2.1.5.1 Variation 1: Preparation of O,N-Acetals by Oxidation

30.1.2.1.5.2 Variation 2: Addition of Alcohols to Alkenyl Bonds

30.1.2.1.5.3 Variation 3: Addition of Amines to Alkenyl Bonds

30.1.2.1.5.4 Variation 4: Nucleophilic Substitution of Alcohols

30.1.2.2 Applications of Product Subclass 2 in Organic Synthesis

30.1.2.2.1 Method 1: Preparation of Acyclic Compounds via C—C Bond Formation with Cleavage of a C—O Bond

30.1.2.2.2 Method 2: Preparation of Cyclic Compounds via C—C Bond Formation with Cleavage of a C—O Bond

30.1.2.2.2.1 Variation 1: C—C Bond Formation Using Organometallic Reagents

30.1.2.2.2.2 Variation 2: C—C Bond Formation Using Allyltrimethylsilane

30.1.2.2.2.3 Variation 3: Insertion of Internal π-Nucleophiles

30.1.2.2.3 Method 3: Reductive Cleavage of the C—O Bond

30.1.2.2.3.1 Variation 1: Reductive Cleavage by Hydrogenation

30.1.2.2.3.2 Variation 2: Reductive Cleavage with Bis(2-methoxyethoxy)aluminum Hydride

30.1.2.2.3.3 Variation 3: Reductive Cleavage with Sodium Borohydride–Boron Trifluoride–Diethyl Ether Complex

30.1.2.2.3.4 Variation 4: Reductive Cleavage with Alane

30.1.2.2.3.5 Variation 5: Reductive Cleavage with Calcium in Liquid Ammonia

30.1.2.2.4 Method 4: Protection of Carbonyl Compounds

30.1.2.2.5 Methods 5: Miscellaneous Transformations

30.1.3 Product Subclass 3: Carbohydrate Derivatives (Including Nucleosides)

H. Yamada

30.1.3 Product Subclass 3: Carbohydrate Derivatives (Including Nucleosides)

30.1.3.1 Synthesis of Product Subclass 3

30.1.3.1.1 Pyrimidine Nucleosides

30.1.3.1.1.1 Method 1: Substitution of Furanosyl Acetates with Silylated Pyrimidines

30.1.3.1.1.2 Method 2: Synthesis from Furanosyl Halides (Hilbert–Johnson Method)

30.1.3.1.1.2.1 Variation 1: Substitution by Silylated Pyrimidines

30.1.3.1.1.2.2 Variation 2: Substitution by Pyrimidine Mercury Salts

30.1.3.1.1.2.3 Variation 3: Activation with Mercury(II) Cyanide in Nitromethane

30.1.3.1.1.3 Method 3: Synthesis from Sulfanylated Furanosides (Thiofuranosides)

30.1.3.1.1.3.1 Variation 1: Synthesis from Sulfinylated Furanosides

30.1.3.1.1.3.2 Variation 2: Intramolecular Glycosylation

30.1.3.1.1.4 Method 4: Synthesis from Furanosyl Trichloroacetimidates

30.1.3.1.1.5 Method 5: Synthesis from Pentenoses

30.1.3.1.1.6 Method 6: Synthesis from N-Furanosyl Derivatives

30.1.3.1.2 Purine Nucleosides

30.1.3.1.2.1 Method 1: Substitution of Furanosyl Acetates with Silylated Purines

30.1.3.1.2.1.1 Variation 1: Fusion of Sugars and Purines

30.1.3.1.2.2 Method 2: Synthesis from Furanosyl Halides

30.1.3.1.2.2.1 Variation 1: Substitution by Purine Silver and Mercury Salts

30.1.3.1.2.3 Method 3: Synthesis from 1-Sulfanylated Furanosides (1-Thiofuranosides)

30.1.3.1.2.3.1 Variation 1: Synthesis from 1-Sulfinylated Furanosides

30.1.3.1.2.4 Method 4: Synthesis from Furanosyl Trichloroacetimidates

30.1.3.1.2.5 Method 5: Synthesis from Pentenoses

30.1.3.1.3 Glycosyl Asparagine Derivatives

30.1.3.1.3.1 Method 1: Synthesis from Glycosyl Azides

30.1.3.1.3.1.1 Variation 1: The Staudinger Reaction

30.1.3.1.3.2 Method 2: Synthesis from Hexenoses

30.1.3.1.3.3 Method 3: Synthesis from Glycosyl Isothiocyanates

30.1.3.1.3.4 Method 4: Synthesis from Pentenyl Glycosides

30.1.3.1.3.5 Method 5: Synthesis from Glycosyl Phenyltrifluoroacetimidates

30.2 Product Class 2: O,P- and S,P-Acetals

M. Yamashita

30.2 Product Class 2: O,P- and S,P-Acetals

30.2.1 Product Subclass 1: O,P-Acetals

30.2.1.1 Synthesis of Product Subclass 1

30.2.1.1.1 Method 1: Addition of Phosphorus Compounds to Ketones or Aldehydes

30.2.1.1.2 Method 2: Substitution Reactions of α,β-Epoxy Phospholane 1-Oxides with Alcohols

30.2.1.1.3 Method 3: Oxidation of 2,3-Dihydro-1H-phosphole 1-Oxides

30.2.1.1.3.1 Variation 1: Using Osmium(VIII) Oxide

30.2.1.1.3.2 Variation 2: Using Peroxides

30.2.1.1.4 Method 4: Addition of Phosphorus Compounds to O,O-Acetals and Related Compounds

30.2.1.1.5 Methods 5: Miscellaneous Methods

30.2.2 Product Subclass 2: S,P-Acetals

30.2.2.1 Synthesis of Product Subclass 2

30.2.2.1.1 Method 1: Reaction of α-Lithio Sulfoxides with Chlorophosphines

30.2.2.1.2 Method 2: Reaction of Trialkyl Phosphites with Cl,S-Acetals

30.2.2.1.3 Method 3: Reaction of α-Lithio Phosphonates or Phosphine Oxides with Sulfur Compounds

30.2.2.1.4 Method 4: Substitution Reactions of 1-Diazoalkylphosphonates

30.2.2.1.5 Method 5: Synthesis from Other S,P-Acetals

30.2.2.1.6 Methods 6: Miscellaneous Methods

30.3 Product Class 3: S,S-Acetals

T.-Y. Luh and M.-k. Leung

30.3 Product Class 3: S,S-Acetals

30.3.1 Product Subclass 1: Acyclic S,S-Acetals

T. Takeda and A. Tsubouchi

30.3.1 Product Subclass 1: Acyclic S,S-Acetals

30.3.1.1 Synthesis of Product Subclass 1

30.3.1.1.1 Method 1: Thioacetalization of Carbonyl and Related Compounds

30.3.1.1.1.1 Variation 1: With Protic Acid Catalysts

30.3.1.1.1.2 Variation 2: With Metal Salt Based Lewis Acid Catalysts

30.3.1.1.1.3 Variation 3: With Other Lewis Acid Catalysts

30.3.1.1.1.4 Variation 4: With Solid Acid Catalysts

30.3.1.1.1.5 Variation 5: In Ionic Liquids

30.3.1.1.1.6 Variation 6: With Functionalized Thiols

30.3.1.1.1.7 Variation 7: With Reagents Other Than Thiols

30.3.1.1.2 Method 2: Conversion of Acetals and Related Compounds

30.3.1.1.2.1 Variation 1: -Acetals

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