Asymmetric hetero-Diels-Alder reaction catalyzed by dirhodium(II) carboxamidates.

Doyle, Michael P; Valenzuela, Marcela; Huang, Penglin · Proc Natl Acad Sci U S A · 2004

basic_science · Level V

Where this comes from

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.

Medical subject headings