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Updated: Jul 15, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Rhodium-catalyzed cascade reaction of 1,6-enynes involving addition, cyclization, and beta-oxygen elimination
Tomoya Miura1, Masahiko Shimada, Masahiro Murakami
1Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan.
Abstract:
The reaction of arylboronic acids with 1,6-enynes that contain an allylic ether moiety is catalyzed by a rhodium(I) complex to produce cyclopentanes with a tetrasubstituted exo olefin and a pendant vinyl group. The reaction is initiated by the regioselective addition of an arylrhodium(I) species to the carbon-carbon triple bond of the 1,6-enyne. The resulting alkenylrhodium(I) compound subsequently undergoes intramolecular carborhodation of the allylic double bond in a 5-exo-trig mode. Beta elimination of the methoxy group affords the cyclization product and the catalytically active methoxorhodium(I) species. The use of alkyl Grignard reagents instead of arylboronic acids as organometallic nucleophiles was also examined.
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