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Construction of Hexahydrophenanthrenes By Rhodium(I)‐Catalyzed Cycloisomerization of Benzylallene‐Substituted Internal Alkynes through C−H Activation
Author(s) -
Kawaguchi Yasuaki,
Yasuda Shigeo,
Mukai Chisato
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201605640
Subject(s) - cycloisomerization , isomerization , rhodium , chemistry , metathesis , catalysis , cyclopropene , medicinal chemistry , benzene , ring (chemistry) , double bond , stereochemistry , photochemistry , organic chemistry , polymerization , polymer
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.