Radicals in Synthesis II fulltext6综合中的部首全文.pdfVIP

Top Curr Chem (2006) 264: 201–236 DOI 10.1007/128_029 © Springer-Verlag Berlin Heidelberg 2006 Published online: 19 January 2006 The Degenerative Radical Transfer of Xanthates and Related Derivatives: An Unusually Powerful Tool for the Creation of Carbon–Carbon Bonds Béatrice Quiclet-Sire · Samir Z. Zard () Laboratoire de Synthèse Organique associé au CNRS, Ecole Polytechnique, 91128 Palaiseau, France zard@poly.polytechnique.fr 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202 2 Some Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204 3 Modifications of the Xanthate Group . . . . . . . . . . . . . . . . . . . . . 209 4 Some Further Synthetic Applications . . . . . . . . . . . . . . . . . . . . . 217 5 Radical-Polar Crossover Reactions . . . . . . . . . . . . . . . . . . . . . . . 222 6 Synthesis of Aromatic Derivatives . . . . . . . . . . . . . . . . . . . . . . . 224 7 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234 Abstract This review summarises recent work on the dithiocarbonyl group transfer re- action. Xanthates, in particular, have proved to be extremely useful for both inter- and intra-molecular 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 radi