Efficient catalytic insertion of acetylenes into a carbon-carbon single bond of nonstrained cyclic compounds under mild conditions
Efficient catalytic insertion of acetylenes into a carbon-carbon single bond of nonstrained cyclic compounds under mild conditions
复制标题
DOI：
10.1021/ja064022i
复制
发表时间：
2006-09-06
影响因子：
15
通讯作者：
Takai, Kazuhiko
中科院分区：
文献类型：
--
作者：
Kuninobu, Yoichiro;Kawata, Atsushi;Takai, Kazuhiko
稀土配合物[REBR(CO)3(THF)]2催化1，3-二羰基环状化合物与乙炔反应，生成中等大小的环状化合物。通过使用异氰化物作为添加剂，Re的催化活性发生了显著的变化，在温和的条件下，乙炔插入到碳−的碳单键中。一个看似合理的机理是，该反应通过形成二苯并环戊烯中间体、通过逆醛缩合反应开环、异构化和还原消除来进行。
A rhenium complex, [ReBr(CO)3(thf)]2, catalyzes the reaction of a 1,3-dicarbonyl cyclic compound with an acetylene to give a medium-sized cyclic compound in excellent yield. By using isocyanide as an additive, the catalytic activity of the rhenium complex changes dramatically, and the insertion of acetylenes into a carbon−carbon single bond occurs under mild conditions. A plausible mechanism is that the reaction proceeds via the formation of a rhenacyclopentene intermediate, ring opening by a retro-aldol reaction, isomerization, and reductive elimination.