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Pentavalent Organobismuth Reagents in Organic Synthesis: Alkylation, Alcohol Oxidation and Cationic Photopolymerization

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Bismuth-Mediated Organic Reactions

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 311))

Abstract

Organic transformations using organobismuth(V) reagents developed by my group are reviewed. The characteristic properties of bismuth, such as the inert pair effect, small bond dissociation energy, and polarized bonding are strongly related to the reactivity of pentavalent organobismuth compounds. The Bi(V) reagents discussed in this chapter include tetraorganylbismuthonium salts ([Ar3RBi+][X−]), triarylbismuth ylides (Ar3Bi=CHCOR), triarylbismuth imides (Ar3Bi=NCOR), triarylbismuth oxides (Ar3Bi=O), and triarylbismuth dichlorides (Ar3BiCl2). These organobismuth(V) compounds are readily accessible in a few steps from triarylbismuthanes (Ar3Bi). New and efficient carbon–carbon bond forming reactions, carbon–heteroatom bond forming reactions, alcohol oxidation, and photoinduced cationic polymerization have been investigated using these reagents. In all these reactions, the good leaving ability as well as the high nucleofugality of the triarylbismuthonio group plays a crucial role in bond-forming and bond-breaking steps.

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Acknowledgements

I deeply thank my coworkers, whose names are listed in the references, for their significant contribution to the chemistry described herein. Most of the research projects were supported by the Grants-in-Aid from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

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  1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan

    Yoshihiro Matano

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  1. Yoshihiro Matano
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Correspondence to Yoshihiro Matano .

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  1. Dépt. Chimie, Université Laval, avenue de la Médecine 1045, Quebec, G1V 0A6, Québec, Canada

    Thierry Ollevier

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Matano, Y. (2011). Pentavalent Organobismuth Reagents in Organic Synthesis: Alkylation, Alcohol Oxidation and Cationic Photopolymerization. In: Ollevier, T. (eds) Bismuth-Mediated Organic Reactions. Topics in Current Chemistry, vol 311. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2011_167

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