Rhodium(I)-Catalyzed Bridged [5+2] Cycloaddition of cis-Allene-vinylcyclopropanes to Synthesize the Bicyclo[4.3.1]decane Skeleton
Rhodium(I)-Catalyzed Bridged [5+2] Cycloaddition of cis-Allene-vinylcyclopropanes to Synthesize the Bicyclo[4.3.1]decane Skeleton
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铑(I)催化桥连[5 2]顺联烯乙烯基环丙烷环加成合成双环[4.3.1]癸烷骨架
DOI：
10.1002/anie.201702288
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发表时间：
2017-07-17
影响因子：
16.6
通讯作者：
Yu, Zhi-Xiang
中科院分区：
文献类型：
--
作者：
Liu, Cheng-Hang;Yu, Zhi-Xiang
此前有报道称，顺-烯-乙烯基环丙烷（cis-ene-VCPs）经铑催化[5+2]反应得到5,7-融合双环产物，其中乙烯基环丙烷（VCP）作为五碳合成物。不幸的是，这种反应的范围非常有限。将顺-烯- vcps的2 pi组分替换为烯段，相应的顺-烯- vcps没有经过预期的正常[5+2]环加成得到5,7-融合的双环产物。相反，具有挑战性的双环[4.3.1]癸烷骨架是通过前所未有的桥式[5+2]环加成得到的。应用DFT计算来理解为什么这种桥接[5+2]反应比预期的但未实现的正常[5+2]反应更有利。
Previously reported was that cis-ene-vinylcyclopropanes (cis-ene-VCPs) underwent Rh-catalyzed [5+2] reaction to give 5,7-fused bicyclic products, where vinylcyclopropane (VCP) acts as five-carbon synthon. Unfortunately, this reaction had very limited scope. Replacing the 2 pi component of cis-ene-VCPs to allene moiety, the corresponding cis-allene-VCPs did not undergo the expected normal [5+2] cycloaddition to give 5,7-fused bicyclic products. Instead, the challenging bicyclo[ 4.3.1]decane skeleton was obtained via an unprecedented bridged [5+2] cycloaddition. DFT calculations were applied to understand why this bridged [5+2] reaction is favored over the anticipated but not realized normal [5+2] reaction.