Quiclet-Sire Béatrice, Zard Samir Z
Laboratoire de Synthèse Organique associé au CNRS (UMR 7652), Département de Chimie, Ecole Polytechnique, 91128 Palaiseau, France.
Chemistry. 2006 Aug 7;12(23):6002-16. doi: 10.1002/chem.200600510.
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).
黄原酸酯及其相关衍生物已被证明对分子间和分子内的自由基加成极为有用。分子间加成到未活化烯烃的广泛适用性为合成带来了巨大机遇,因为各种官能团可以在温和条件下汇聚在一起,复杂结构也能迅速组装起来。产物中黄原酸酯的存在对于通过自由基和非自由基途径进行进一步修饰而言也是一项强大的优势。特别重要的是能够获得高度取代的芳香族和杂芳香族衍生物,以及通过由各种含硫代羰基硫基的试剂介导的可控自由基聚合反应(可逆加成-断裂链转移聚合和金属介导的活性自由基聚合过程)合成嵌段聚合物。