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Fused‐Ring Formation by an Intramolecular “Cut‐and‐Sew” Reaction between Cyclobutanones and Alkynes
Author(s) -
Deng Lin,
Jin Likun,
Dong Guangbin
Publication year - 2018
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.201712487
Subject(s) - intramolecular force , decarbonylation , chemistry , steric effects , cyclohexenone , stereochemistry , ligand (biochemistry) , phosphine , ring (chemistry) , bond cleavage , catalysis , organic chemistry , biochemistry , receptor
The development of a catalytic intramolecular “cut‐and‐sew” transformation between cyclobutanones and alkynes to construct cyclohexenone‐fused rings is described herein. The challenge arises from the need for selective coupling at the more sterically hindered proximal position, and can be addressed by using an electron‐rich, but less bulky, phosphine ligand. The control experiment and 13 C‐labelling study suggest that the reaction may start with cleavage of the less hindered distal C−C bond of cyclobutanones, followed by decarbonylation and CO reinsertion to enable Rh insertion at the more hindered proximal position.