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Updated: Aug 25, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Asymmetric hetero-Diels-Alder reaction catalyzed by dirhodium(II) carboxamidates
Michael P Doyle1, Marcela Valenzuela, Penglin Huang
1Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, USA. mdoyle3@umd.edu
Abstract:
Chiral dirhodium(II) carboxamidates are highly efficient catalysts for reactions between a variety of aldehydes and activated dienes. Catalyst loadings as low at 0.01 mol % have been realized with enantioselectivities up to 97%. Kinetic investigations reveal a pronounced electronic influence on the rate of the hetero-Diels-Alder reaction with a Hammett rho value of +1.9 (versus sigma(+)). Inhibition of the catalyst by reactant aldehyde is apparent, but reactions show first-order dependence on aldehyde and diene, and there is a variable dependence on catalyst.
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