Hydrosilylation heteroatomic compounds

The author hopes that this chapter has convinced the readers of the value of homogeneous catalysis for the synthesis of organophosphorus compounds and for organo-heteroatom compounds in a broader sense. Hydrosilylation and hydroboration are indispensable modern synthetic reactions in this category. The H-P addition reactions herein described joins them as a third member. Although this chapter does not cover, the addition reactions of the S-P and Se-P bonds in thiophosphates [39] and selenophosphates [40] to alkynes also proceed in the presence of transition metal catalysts. In view of the wide use of phosphorus compounds, the new procedures will find practical applications. 

Trichlorosilanes are readily transformed to the pentafluorosilicate compounds (100) and (101) by reaction with excess potassium fluoride. The C—Si bond of the hexavalent organosilicon species is converted into a C—X (X = halogen or heteroatom like hydroxy and alkoxy) or a C—C bond. Thus, through the hydrosilylation reaction net transformations of alkenes and alkynes to halides, ethers and alcohols, as well as the construction of carbon frameworks, is easily achieved (Scheme 18). ... 

The hydrosilylation of carbon-heteroatom multiple bonds had received little attention until it was found in 1972 that Rh(PPh3)3Cl is an extremely effective catalyst for the hydrosilylation of carbonyl compounds. This is a new and unique reduction method since the resulting silicon-oxygen bond can easily be hydrolyzed. Other transition metal complexes including platinum, ruthenium , and rhodium also have good catalytic activity in the selective and asymmetric hydrosilylation of carbonyl compounds "". 

---