Copper(I)-catalyzed substitution reactions of propargylic amines: importance of C(sp)-C(sp3) bond cleavage in generation of iminium intermediates.
Copper(I)-catalyzed substitution reactions of propargylic amines: importance of C(sp)-C(sp3) bond cleavage in generation of iminium intermediates.
复制标题
DOI：
10.1021/ja9109055
复制
发表时间：
2010-03
影响因子：
15
通讯作者：
Tsuyuka Sugiishi;Akifumi Kimura;Hiroyuki Nakamura
中科院分区：
文献类型：
--
作者：
Tsuyuka Sugiishi;Akifumi Kimura;Hiroyuki Nakamura
炔丙胺的取代反应在铜（I）催化剂的存在下进行。机理研究表明，氮孤对电子辅助下的C（sp）-C（sp（3））键断裂是反应的关键，生成的亚胺中间体经历了胺交换、醛交换和炔加成反应。由于亚胺中间体是炔-炔-胺（A（3））偶联反应的关键，因此这种转化不仅对于炔丙胺的重构有效，而且对于在手性催化剂存在下外消旋化合物的手性诱导也有效。
Substitution reactions of propargylic amines proceed in the presence of copper(I) catalysts. Mechanistic studies showed that C(sp)-C(sp(3)) bond cleavage assisted by nitrogen lone-pair electrons is essential for the reaction, and the resulting iminium intermediates undergo amine exchange, aldehyde exchange, and alkyne addition reactions. Because iminium intermediates are key to aldehyde-alkyne-amine (A(3)) coupling reactions, this transformation is effective not only for reconstruction of propargylic amines but also for chiral induction of racemic compounds in the presence of chiral catalysts.