Regio- and Enantioselective Rhodium-Catalyzed Addition of 1,3-Diketones to Allenes: Construction of Asymmetric Tertiary and Quaternary All Carbon Centers

Angew Chem Int Ed Engl. 2017 Feb 6;56(7):1903-1907. doi: 10.1002/anie.201610577. Epub 2017 Jan 11.

Abstract

An unprecedented highly regio- and enantioselective rhodium-catalyzed addition of 1,3-diketones to terminal and 1,1-disubstituted allenes furnishing asymmetric tertiary and quaternary all-carbon centers is reported. By applying a RhI /phosphoramidite/TFA catalytic system under mild conditions, the desired chiral branched α-allylated 1,3-diketones could be obtained in good to excellent yields, with perfect regioselectivity and in high enantioselectivity. The reaction shows a broad functional-group tolerance on both reaction partners highlighting its synthetic potential.

Keywords: 1,3-diketones; allenes; asymmetric catalysis; rhodium; γ,δ-unsaturated ketones.

Publication types

  • Research Support, Non-U.S. Gov't