Hua Ruimao, Takeda Hideaki, Onozawa Shun-ya, Abe Yoshimoto, Tanaka Masato
Department of Chemistry, Tsinghua University, Beijing 100084, China.
Org Lett. 2007 Jan 18;9(2):263-6. doi: 10.1021/ol062686r.
Allylic sulfides add to alkynes in the presence of nickel complexes efficiently to afford thio-1,4-dienes regio- and stereoselectively. Functional groups such as alkoxy, siloxy, hydroxy, carboalkoxy, chloro, and cyano groups are tolerated. A mechanism that involves a pi-allyl nickel intermediate is proposed on the basis of isolation of pi-allyl complexes and distribution of products in the reactions of alpha- or gamma-methylated allyl sulfide. [reaction: see text].
在镍配合物存在下，烯丙基硫化物能有效地与炔烃加成，区域和立体选择性地生成硫代-1,4-二烯。诸如烷氧基、硅氧基、羟基、烷氧羰基、氯和氰基等官能团均可耐受。基于π-烯丙基配合物的分离以及α-或γ-甲基化烯丙基硫化物反应中产物的分布，提出了一种涉及π-烯丙基镍中间体的机理。[反应：见正文]
