PtCl2-catalyzed conversion of 1,6- and 1,7-enynes to 1-vinylcycloalkenes. Anomalous bond connection in skeletal reorganization of enynes
PtCl2-catalyzed conversion of 1,6- and 1,7-enynes to 1-vinylcycloalkenes. Anomalous bond connection in skeletal reorganization of enynes
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DOI：
10.1021/om950832j
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发表时间：
1996-02-06
期刊：
影响因子：
2.8
通讯作者：
Murai, S
中科院分区：
文献类型：
--
作者：
Chatani, N;Furukawa, N;Murai, S
在80 ℃下，在甲苯中用催化量的PtCl 2处理1，6-和1，7-烯炔，导致烯炔的快速重组（环重排），以高产率得到1-乙烯基环烯烃。氘标记实验表明，两个机制的路径操作的环重排。取代基的性质和位置影响反应进程。在末端炔属碳具有酯基的1，6-烯炔的反应中选择性地获得异常碳-碳键的形成。
The treatment of 1,6- and 1,7-enynes with a catalytic amount of PtCl2 in toluene at 80 degrees C results in sheletal reorganization (cyclorearrangement) of the enynes to give 1-vinylcycloalkenes in high yields. A deuterium labeling experiment indicates that two mechanistic paths are operating for the cyclorearrangement. The nature and position of substituents affect the reaction course. Anomalous carbon-carbon bond formation is attained selectively in the reaction of 1,6-enynes having an, ester group at the terminal acetylenic carbon.