Construction of Hexahydrophenanthrenes By Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Substituted Internal Alkynes through C-H Activation.
Construction of Hexahydrophenanthrenes By Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Substituted Internal Alkynes through C-H Activation.
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DOI：
10.1002/anie.201605640
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发表时间：
2016-08
影响因子：
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通讯作者：
Yasuaki Kawaguchi;S. Yasuda;C. Mukai
中科院分区：
文献类型：
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作者：
Yasuaki Kawaguchi;S. Yasuda;C. Mukai
用[RhCl（CO）2 ]2处理苄基联二烯取代的内炔，通过C（sp（2））-H键的活化实现了一种新的环化异构化反应，生成了六氢菲衍生物。该反应可能通过连续形成rhodabicyclo[4.3.0]中间体、苯环上的C（sp（2））-H键与C（sp（2））-Rh（III）键之间的σ-键复分解以及三种σ-、π-和σ-烯丙基铑（III）物种之间的异构化进行，这是基于氘代底物的实验提出的。
The treatment of benzylallene-substituted internal alkynes with [RhCl(CO)2 ]2 effects a novel cycloisomerization by C(sp(2) )-H bond activation to produce hexahydrophenanthrene derivatives. The reaction likely proceeds through consecutive formation of a rhodabicyclo[4.3.0] intermediate, σ-bond metathesis between the C(sp(2) )-H bond on the benzene ring and the C(sp(2) )-Rh(III) bond, and isomerization between three σ-, π-, and σ-allylrhodium(III) species, which was proposed based on experiments with deuterated substrates.