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Updated: Jul 18, 2026
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Cycloisomerization of enynes via rhodium vinylidene-mediated catalysis
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
Abstract:
A novel rhodium-catalyzed cycloisomerization has been developed which converts various acyclic enynes to their cyclic diene isomers with endoselectivity. Both [RhCl(COD)]2/P(4-FC6H4)3 and RhCl(PPh3)3 catalyst systems are effective in promoting the C-C bond-forming cyclization of enynes to furnish carbo- and heterocycles in good to excellent yield. Deuterium labeling studies suggest that the reaction proceeds through the formation of a rhodium vinylidene followed by subsequent [2 + 2] cycloaddition with the alkene and ring-opening of the resulting rhodacyclobutane. These mechanistic studies reevaluate a previously proposed reaction pathway and lead to the discovery of a new cycloisomerization reaction that involves migration of silyl and selenyl substituents at the alkyne of enyne substrates upon cyclization.
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