Riding the tiger: Using degeneracy to tame wild radical processes

Abstract

Xanthates are convenient precursors of a variety of radicals that can be captured in an inter- or intramolecular fashion. Overall, the process involves rupture of the sulfide C-S bond and addition of the elements of the xanthate to the olefinic trap. The xanthate in the product can be reductively removed in some cases simply by heating in isopropanol with stoichiometric amounts of dilauroyl peroxide. A new radical allylation reaction based on allyl sulfones has also been devised where, in a manner similar to that with xanthates, a number of degenerate steps force the reaction in the desired direction.