Cationic bismuth-catalyzed hydroamination and direct substitution of the hydroxy group in alcohols with amides

Abstract

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 3CN) 4PF 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. © 2011 Springer-Verlag Berlin Heidelberg.