Some intriguing mechanistic aspects of the radical chemistry of xanthates

Xanthates are exceedingly useful substrates for intermolecular and intramolecular radical additions, even to unactivated alkenes. Various functional groups can be brought together under mild, neutral conditions, thus providing tremendous opportunities for organic synthesis. Because the products of the addition-transfer process are also xanthates, iteration allows the formation of block polymers by a controlled radical polymerisation (the RAFT/MADIX technology). The present overview concentrates on mechanistic and unexpected aspects of this chemistry, which may be of particular interest to physical organic chemists.