Matsunaga Shigeki, Shibasaki Masakatsu
The University of Tokyo, Hongo, Tokyo, Japan.
Top Curr Chem. 2012;311:179-97. doi: 10.1007/128_2011_169.
Bismuth-catalyzed hydroamination and direct substitution of the hydroxy group in alcohols are described in this chapter. Intermolecular 1:1 hydroamination of 1,3-dienes with carbamates, sulfonamides, and carboxamides was promoted by a combination of Bi(OTf)(3) and Cu(CH(3)CN)(4)PF(6). The mechanistic studies suggested that a cationic bismuth species would be an active species, which selectively promotes 1:1 hydroamination to give allylic amides in up to 96% yield. The cationic bismuth species was also applicable for hydroamination of vinyl arenes. The combination of Bi(OTf)(3) and KPF(6) was an excellent catalyst for direct substitution of the hydroxy group in allylic, propargylic, and benzylic alcohols with carbamates, sulfonamides, and carboxamides, giving allylic, propargylic, and benzylic amides, respectively, in up to 99% yield in one step.
本章介绍了铋催化的氢胺化反应以及醇类中羟基的直接取代反应。Bi(OTf)₃和Cu(CH₃CN)₄PF₆的组合促进了1,3 - 二烯与氨基甲酸酯、磺酰胺和羧酰胺的分子间1:1氢胺化反应。机理研究表明，阳离子铋物种可能是活性物种，它能选择性地促进1:1氢胺化反应，以高达96%的产率得到烯丙基酰胺。阳离子铋物种也适用于乙烯基芳烃的氢胺化反应。Bi(OTf)₃和KPF₆的组合是将烯丙醇、炔丙醇和苄醇中的羟基直接用氨基甲酸酯、磺酰胺和羧酰胺进行取代的优良催化剂，一步反应分别以高达99%的产率得到烯丙基、炔丙基和苄基酰胺。
