Discovery and synthetic applications of novel silicon-carbon bond cleavage reactions based on the coordination number change of organosilicon compounds.

Some synthetically useful transformations of organosilicon compounds have been developed since the mid 1970s, based on the new concept that the silicon-carbon bonds are activated toward electrophilic cleavage via the formation of penta- and hexa-coordinate species. This review mainly consists of the following aspects: (1) a general concept for the activation of the silicon-carbon bond via penta- and hexa-coordinate species, (2) synthetic application of hexa-coordinate organopentafluorosilicates, and (3) development of the H(2)O(2) oxidation of the silicon-carbon bond and its synthetic applications via the intramolecular hydrosilylation, silicon-tethered intramolecular radical cyclization and Diels-Alder reaction, and some silicon-containing organometallic reagents for nucleophilic hydroxymethylation and hydroxyallylation synthons.(Communicated by Hitosi NOZAKI, M.J.A.).