Iodine-Catalyzed Chemoselective C-N Bond-Forming Reactions Using Benzylic or Cinnamyl Alcohols with Heterocyclic Thiols and Thiones.

A chemoselective formation of C-N bond catalyzed by iodine has been developed using heterocyclic thiols and thiones. The reaction occurs at the nitrogen center over the sulfur, leading to the amination against the traditional sulfenylation. A wide variety of allylic and benzylic alcohols serve as coupling partners. This method showed a good tolerance toward 1 H-tetrazole-5-thiol, 5-methyl-1,3,4-thiadiazole-2-thiol, benzo[ d]thiazole-2(3 H)-thione, and benzo[ d]oxazole-2(3 H)-thione derivatives.