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The Degenerative Radical Transfer of Xanthates and Related Derivatives: An Unusually Powerful Tool for the Creation of Carbon–Carbon Bonds

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Radicals in Synthesis II

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 264))

Abstract

This review summarises recent work on the dithiocarbonyl group transfer reaction. 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 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 dithiocarbonyl agents (RAFT and MADIX processes).

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Abbreviations

AIBN:

azo-bis(isobutyronitrile)

ACCN:

azo-bis(cyclohexanecarbonitrile)

DCE:

1,2-dichloroethane

PMB:

p-methoxybenzyl

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Acknowledgments

We are deeply grateful to our students and collaborators, whose names appear in the references, and who made this chemistry possible through their hard work and dedication. We also thank the following organisations and companies who have provided financial support over the years: Ecole Polytechnique, CNRS, DGA, MNRT, the Alfred Kastler Foundation, the Royal Commission for the Exhibition of 1851, CONACyT (Mexico), MECyD (Spain), Rhodia, and Sanofi-Aventis.

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Authors and Affiliations

  1. Laboratoire de Synthèse Organique associé au CNRS, Ecole Polytechnique, 91128, Palaiseau, France

    Béatrice Quiclet-Sire & Samir Z. Zard

Authors
  1. Béatrice Quiclet-Sire
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  2. Samir Z. Zard
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Correspondence to Samir Z. Zard .

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Andreas Gansäuer

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Quiclet-Sire, B., Zard, S.Z. The Degenerative Radical Transfer of Xanthates and Related Derivatives: An Unusually Powerful Tool for the Creation of Carbon–Carbon Bonds. In: Gansäuer, A. (eds) Radicals in Synthesis II. Topics in Current Chemistry, vol 264. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_029

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