Construction of Hexahydrophenanthrenes By Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Substituted Internal Alkynes through C−H Activation
Yasuaki Kawaguchi
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192 Japan
Search for more papers by this authorDr. Shigeo Yasuda
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Chisato Mukai
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192 Japan
Search for more papers by this authorYasuaki Kawaguchi
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192 Japan
Search for more papers by this authorDr. Shigeo Yasuda
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Chisato Mukai
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192 Japan
Search for more papers by this authorAbstract
The treatment of benzylallene-substituted internal alkynes with [RhCl(CO)2]2 effects a novel cycloisomerization by C(sp2)−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(sp2)−H bond on the benzene ring and the C(sp2)−RhIII bond, and isomerization between three σ-, π-, and σ-allylrhodium(III) species, which was proposed based on experiments with deuterated substrates.
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