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Rhodium(I)‐Catalyzed Cycloisomerization of Benzylallene‐Alkynes through CH Activation
Author(s) -
Kawaguchi Yasuaki,
Yasuda Shigeo,
Kaneko Akira,
Oura Yuki,
Mukai Chisato
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201403990
Subject(s) - cycloisomerization , rhodium , chemistry , catalysis , medicinal chemistry , electrophile , stereochemistry , organic chemistry
The efficient Rh I ‐catalyzed cycloisomerization of benzylallene‐alkynes produced the tricyclo[9.4.0.0 3,8 ]pentadecapentaene skeleton through a C sp 2H bond activation in good yields. A plausible reaction mechanism proceeds via oxidative addition of the acetylenic CH bond to Rh I , an ene‐type cyclization to the vinylidenecarbene–Rh I intermediate, and an electrophilic aromatic substitution with the vinylidenecarbene species. It was proposed based on deuteration and competition experiments.