OXIDATIVE CLEAVAGE OF SILICON-CARBON BONDS IN ORGANOSILICON FLUORIDES TO ALCOHOLS

Article abstract of DOI:10.1016/S0040-4020(01)88597-5

Certain functional silyl groups have been shown to be synthetically equivalent to the OH group.All of the C-Si bonds in organosilicon fluorides, K2 and R_nSiF4-n (n=1,2,3) are cleaved by m-chloroperbenzoic acid (MCPBA) in DMF to give the corresponding alcohols in high yields.Although the reaction with RSiF5(2-) and RSiF3 proceeds without any additive, cleavage of R2SiF2 and R3SiF requires, respectively, a catalytic or excess amount of KF.A triorganoethoxysilane also undergoes similar oxidative cleavage reactions in the presence of an excess amount of KF.The MCPBA-oxidation of exo- and endo-2-norbornyl-silicate and -trifluorosilane proceeds stereospecifically with retention of configuration at carbon.A remarkable solvent effect has been observed in the oxidative cleavage of RSiF3.A plausible mechanism involves a hexacoordinate silicon species in which the organic group intramolecularly migrates from Si to O of the coordinated MCPBA.