Controlling the α/γ-Reactivity of Vinylogous Ketone Enolates in Organocatalytic Enantioselective Michael Reactions.

Angew Chem Int Ed Engl

Departamento de Química Orgánica I, Universidad del País Vasco UPV/EHU, Manuel Lardizabal 3, 20018, San Sebastián, Spain.

Published: July 2017

The first regio-, diastereo-, and enantioselective direct Michael reaction of β,γ-unsaturated ketones with nitroolefins is enabled by Brønsted base/hydrogen-bonding bifunctional catalysis. A squaramide-substituted tertiary amine catalyzes the reaction of a broad range of β,γ-unsaturated ketones to proceed at the α-site exclusively, giving rise to adducts with two consecutive tertiary carbon stereocenters in diastereomeric ratios of up to >20:1 and enantioselectivities generally in the 90-98 % ee range.

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http://dx.doi.org/10.1002/anie.201703764DOI Listing

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