Atom and group transfer reactions

Abstract

Abstract The accidental discovery by Kharasch and his students of the dramatic effect of oxygen or peroxides on the course of the addition of hydrogen bromide to olefins (cf. Scheme 1.4) is an important watershed in the history of radical chemistry, not only because it established conclusively the role of free radicals as reactive intermediates in solution, but also because this early example of a chain process is the prototype for a large number of exceedingly useful reactions (reviews: Stacey and Harris 1963; Walling and Huyser 1963; Sosnovsky 1964). In fact, many of the radical reactions of organo-tin, -germanium, and -silicon hydrides that we have seen in the earlier chapters may be viewed as particular cases of the ‘Kharasch-type’ atom or, more generally, group transfer process.