Matano Yoshihiro
Department of Molecular Engineering, Kyoto University, Nishikyo-ku, Kyoto, Japan.
Top Curr Chem. 2012;311:19-44. doi: 10.1007/128_2011_167.
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 ([Ar(3)RBi(+)][X(-)]), triarylbismuth ylides (Ar(3)Bi=CHCOR), triarylbismuth imides (Ar(3)Bi=NCOR), triarylbismuth oxides (Ar(3)Bi=O), and triarylbismuth dichlorides (Ar(3)BiCl(2)). These organobismuth(V) compounds are readily accessible in a few steps from triarylbismuthanes (Ar(3)Bi). 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.
本文综述了我研究小组开发的使用有机铋（V）试剂的有机转化反应。铋的特性，如惰性电子对效应、小的键离解能和极化键，与五价有机铋化合物的反应性密切相关。本章讨论的Bi（V）试剂包括四芳基铋鎓盐（[Ar(3)RBi(+)][X(-)]）、三芳基铋叶立德（Ar(3)Bi=CHCOR）、三芳基铋酰亚胺（Ar(3)Bi=NCOR）、三芳基铋氧化物（Ar(3)Bi=O）和三芳基二氯化铋（Ar(3)BiCl(2)）。这些有机铋（V）化合物可以通过几步反应从三芳基铋烷（Ar(3)Bi）轻松制得。使用这些试剂研究了新型高效的碳-碳键形成反应、碳-杂原子键形成反应、醇氧化反应和光诱导阳离子聚合反应。在所有这些反应中，三芳基铋鎓基团良好的离去能力以及高亲核性在成键和断键步骤中起着关键作用。
