Tin in Organic Synthesis

Tin in Organic Synthesis is a systematic presentation of the organic chemistry of tin. This book discusses the significant advances that have been made with regard to the applications of organotin compounds as reagents or intermediates in organic synthesis and points out directions for future developments. This monograph is comprised of 17 chapters divided into four sections. Following a brief introduction to organotin chemistry, the production of the organotin reagents, which are most usually employed in organic synthesis, is described. Special emphasis is placed on the creation of a fresh tin-carbon bond, a preliminary step in numerous fruitful applications. The following chapters are devoted to synthetic applications involving tin-hydrogen, tin-carbon, and tin-heteroatom bonds. The reduction of organic halides, carbonyl compounds, thio, nitrogen compounds, unsaturated carbon-carbon bonds, and seleno and telluro compounds is considered. The discussion then turns to electrophilic cleavages of tin-carbon bonds, which are of possible interest in organic synthesis, along with transmetallation and metallation of organotin compounds. The creation of new carbon-carbon bonds through substitution, addition, or elimination reactions is also examined. The remaining chapters focus on organotin alkoxides, organotin enolates, organotin oxides and peroxides, and organotin esters. This book will be of interest to students and researchers in the field of organic chemistry.

Part One: Introduction to Organotin Chemistry

1 General Organotin Chemistry

1.1 Nomenclature

1.2 Literature

1.3 Tin and its Bonds

1.4 Some Physical Data

1.5 Toxicity and Hazards

2 Preparation of Organotin Reagents

2.1 Synthesis of Basic Organotin Reagents

2.2 Creation of a Fresh Tin-Carbon Bond

2.3 Functional Transformations of Groups Bound to Tin

References

Part Two: Synthetic Applications Involving Tin-Hydrogen Bonds

3 Reduction of Organic Halides

3.1 General

3.2 Reduction of Simple Organic Halides and Polyhalides

3.3 Chemoselective Reduction of Polyfunctional Halides

3.4 Stereochemistry

3.5 Reductions with Free-Radical Rearrangement or Fragmentation

4 Reduction of Carbonyl Compounds

4.1 Aldehydes and Ketones

4.2 Acyl Halides

4.3 Esters and Related Compounds

5 Reduction of Thio, Seleno and Telluro Compounds

5.1 Thio Derivatives

5.2 Seleno Derivatives

5.3 Telluro Derivatives

6 Reduction of Nitrogen Compounds

6.1 Isocyanides, Isocyanates and Related Compounds

6.2 Nitro Compounds

6.3 Miscellaneous Reactions

7 Reduction of Unsaturated Carbon-Carbon Bonds

7.1 αβ-Unsaturated Ketones and Aldehydes

7.2 αβ-Unsaturated Nitriles and Esters

7.3 Functionalization via Mercuric Compounds

References

Part Three: Synthetic Applications Involving Tin-Carbon Bonds

8 Access to Carbon-Hydrogen and Carbon-Heteroatom Bonds

8.1 Carbon-Hydrogen Bonds

8.2 Carbon-Halogen Bonds

8.3 Carbon-Oxygen Bonds; Related Oxidation Reactions

8.4 Other Carbon-Heteroatom Bonds

9 Transmetallation and Metallation of Organotin Compounds

9.1 General Features of Transmetallation and Metallation Reactions

9.2 Transmetallation of Vinyl Organotin Compounds

9.3 Transmetallation of α-Heterosubstituted Organotin Compounds

9.4 Transmetallation of Benzyl- and Allyl-Tin Compounds

9.5 Transmetallation of Miscellaneous Organotin Compounds

9.6 Metallation of Organotin Compounds

10 Access to Carbon-Carbon Bonds

10.1 Via Substitution Reactions

10.2 Via Addition Reactions

10.3 Via Elimination Reactions

References

Part Four: Synthetic Applications Involving Tin-Heteroatom Bonds

11 Organotin Alkoxides

11.1 In Substitution Reactions

11.2 In Oxidation Reactions

11.3 In Addition Reactions

11.4 As Catalysts

12 Organotin Enolates

12.1 Organotin(IV) Enolates

12.2 Tin(II) Enolates

13 Organotin Oxides and Peroxides

13.1 Oxides

13.2 Peroxides

14 Organotin Esters

14.1 Carboxylates

14.2 Other Esters

15 Organotin Compounds with Tin-Nitrogen Bonds

15.1 Simple Amines

15.2 Other Compounds with Sn-N Bonds

16 Organotin Compounds with Tin-Sulphur Bonds

16.1 Synthesis of Sulphides

16.2 Synthesis of Thiol Esters

16.3 Synthesis of Acylsulphenyl Chlorides

16.4 Conversion of Carbonyl to Thiocarbonyl Units

17 Organotin Compounds with Tin Bonds to Miscellaneous Elements

17.1 Tin-Tin Bonds

17.2 Tin-Metal Bonds

17.3 Tin-Halogen Bonds

References

Index