Oxygen Atom Transfer from Silyl Hydroperoxide. Chlorohydrin Formation

Abstract

In the context of developing synthetic reactions based on the HSAB principle¹, it was discerned that triorganosilyl hydroperoxides possess a similar bonding arrangement to that found in percarboxylic acids; both types of compounds being made up of a soft acid-soft base pair with respect to the 0-0 linkage. In addition, acyl and triorganosilyl groups may be considered as functionally equivalent since both are hard acid centers capable of accepting electrons. In the acyl group, excess electrons can be displaced toward the oxygen end, whereas silicon avails itself of vacant d orbitals to accomodate the negative charge.