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Updated: Apr 29, 2026

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
3-Acyloxy-1,4-enyne: a New Five-carbon Synthon for Rhodium-Catalyzed (5+2) Cycloadditions
Casi M Schienebeck1, Xiaoxun Li1, Xing-Zhong Shu1
1School of Pharmacy and Department of Chemistry, University of Wisconsin, Madison, WI 53705, USA.
Abstract:
Seven-membered rings are ubiquitous in natural products and pharmaceutical agents and their syntheses continue to stimulate the development of novel synthetic methods. The (5+2) cycloaddition is one of the most efficient ways to access seven-membered rings since the 2-carbon components (alkenes, alkynes, or allenes) are readily available. Prior to our study, however, there was only one type of transition metal-catalyzed (5+2) cycloaddition: the reaction between vinylcyclopropanes and alkenes, alkynes, or allenes. We recently developed a new type of transition metal-catalyzed (5+2) cycloaddition, where the 5-carbon building block is 3-acyloxy-1,4-enyne (ACE). Our recent progress on Rh-catalyzed intra- and intermolecular (5+2) cycloadditions of ACEs and alkynes is summarized in this article. Using chiral propargylic esters, bicyclic products were prepared in high optical purity by the intramolecular (5+2) cycloadditions. Monocyclic seven-membered rings were synthesized by intermolecular (5+2) cycloaddition of ACEs and alkynes. Kinetic studies indicated that the rate of this intermolecular cycloaddition was significantly accelerated when the acetate was replaced by dimethylaminobenzoate. DFT calculations suggested that novel metallacycles were generated by a Rh-promoted oxidative cycloaddition of 1,4-enynes accompanied by a 1,2-acyloxy migration of propargylic esters.
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