title: Construction of Hexahydrophenanthrenes By Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Substituted Internal Alkynes through C-H Activation.
abstract: 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.
authors.affiliation: Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.
authors.forename: Yasuaki
authors.initials: Y
authors.lastname: Kawaguchi
authors.affiliation: Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.
authors.forename: Shigeo
authors.initials: S
authors.lastname: Yasuda
authors.affiliation: Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan. mukai@p.kanazawa-u.ac.jp.
authors.forename: Chisato
authors.initials: C
authors.lastname: Mukai
keywords: C−H activation; alkynes; allenes; cycloisomerization; rhodium