Powerful CarbonCarbon Bond Forming Reactions Based on a Novel Radical Exchange Process

Xanthates and related derivatives have proved to be extremely useful for both inter‐ and intramolecular radical additions. The broad applicability of the intermolecular addition to un‐activated olefins opens tremendous opportunities for synthesis, since various functional groups can be brought together under mild conditions and complex structures can be rapidly assembled. The presence of the xanthate in the product is also a powerful asset for further modifications, by both radical and non‐radical pathways. Of special importance is the access to highly substituted aromatic and heteroaromatic derivatives and the synthesis of block polymers through a controlled radical polymerisation mediated by various thiocarbonylthio group containing agents (RAFT and MADIX processes).