Organosilicon compounds illustrative syntheses

This chapter describes the application of iridium-catalyzed reactions in the synthesis of molecular and macromolecular organosilicon compounds and related sihcon derivatives. Some mechanistic implications are introduced which illustrate the specific catalytic activation of organic and silicon compounds by iridium... 

Stereoselective enzymatic hydrolyses of esters represent a further type of biotransformation that has been used for the synthesis of optically active organosilicon compounds. The first example of this particular type of bioconversion is illustrated in Scheme 15. Starting from the racemic (l-acetoxyethyl)silane rac-11, the optically active (l-hydroxyethyl)silane (5)-41 was obtained by a kinetic racemate resolution using porcine liver esterase (PLE E.C. 3.1.1.1) as the biocatalyst7. The silane (5)-41 (isolated with an enantiomeric purity of 60% ee bioconversion not optimized) is the antipode of compound (R)-41 which was obtained by an enantioselective microbial reduction of the acetylsilane 40 (see Scheme 8). 

This short text is intended to introduce the student of synthetic organic chemistry to the reactions of organoboron and organosilicon compounds which have been exploited by organic chemists, and to illustrate how these reactions have been applied to problems in organic synthesis. It is hoped that the chemistry described in this slim volume will encourage students to consult the more comprehensive reference texts and reviews available. These are listed in the bibliographies at the end of each section. 

In view of the importance currently attached to the synthesis of homochiral organic molecules, examples which illustrate the use of organoboron and organosilicon compounds in this area are included where appropriate. 

Our interests in highly unsymmetrical organosilicon compounds were along other lines, and one incentive was the development of syntheses of unsymmetrical compounds with low melting points. A selected illustration is the synthesis of phenyl-o-tolyl-w-tolyl-p-tolysilane. 

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