Catalyzed intramolecular olefin insertion into a carbon-carbon single bond
Catalyzed intramolecular olefin insertion into a carbon-carbon single bond
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DOI：
10.1021/ja021062n
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发表时间：
2002-11-27
影响因子：
15
通讯作者：
Ito, Y
中科院分区：
文献类型：
--
作者：
Murakami, M;Itahashi, T;Ito, Y
分子内C-−C双键插入C-−-C单键是通过在阳离子Rh(I)-DPP络合物的催化量下处理3-位含苯乙烯基的环丁酮来实现的。最初，在环丁酮的羰基碳和α-碳之间插入Rh。乙烯基团的分子内配位导致其迁移插入C−Rh键。还原消除得到苯并双环[3.2.1]辛烷-3-酮。值得注意的是，当用DPP代替DPP时，得到了开环的α，β不饱和酮。在这个反应中，Rh断裂了环丁酮的αsp3碳和βsp3碳之间的键。配位的乙烯基团指导着用dppe配体观察到的这种新的区域选择性切割。
Intramolecular insertion of a C−C double bond into a C−C single bond was achieved by treatment of cyclobutanone bearing ano-styryl group at the 3-position with a catalytic amount of a cationic rhodium(I)-dppp complex. Initially, rhodium is inserted between the carbonyl carbon and the α-carbon of the cyclobutanone. Intramolecular coordination of the vinyl group results in its migratory insertion into the C−Rh linkage. Reductive elimination affords benzobicyclo[3.2.1]octan-3-one. Notably, a ring-opened α,β-unsaturated ketone was obtained when dppe was used instead of dppp. In this reaction, rhodium cleaved the bond between the α sp3carbon and the β sp3carbon of the cyclobutanone. The coordinating vinyl group directs this new regioselectivity of cleavage observed with the dppe ligand.