通过 C-H 活化的 Rh 催化苄基烯丙基内炔烃的环异构化反应的机理研究。
Mechanistic Investigation of Rh-Catalyzed Cycloisomerization of Benzylallene-Internal Alkynes via C-H Activation.
机构信息
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University , Kakuma-machi, Kanazawa 920-1192, Japan.
出版信息
J Org Chem. 2017 Jul 21;82(14):7666-7674. doi: 10.1021/acs.joc.7b01048. Epub 2017 Jul 6.
Treatment of the benzylallene-internal alkynes with [RhCl(CO)] effected a cycloisomerization via a C-H bond activation to produce the tricyclo[9.4.0.0]pentadecapentaene skeleton. The reaction mechanism via formation of the rhodabicyclo[4.3.0] intermediates and σ-bond metathesis between the C-H bond on the benzene ring and the C-Rh bond was proposed. In addition, a plausible alternative mechanism for the previously reported cycloisomerization of the benzylallene-terminal alkynes could also be proposed.
用[RhCl(CO)]处理苄基内炔，通过 C-H 键活化进行环异构化，生成三环[9.4.0.0]pentadecapentaene 骨架。通过形成铑双环[4.3.0]中间体和苯环上的 C-H 键与 C-Rh 键之间的σ键重排，提出了反应机理。此外，还可以提出一个合理的替代机制来解释以前报道的苄基烯丙基末端炔烃的环异构化反应。
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