Science 2010-02-19

Asymmetric cooperative catalysis of strong Brønsted acid-promoted reactions using chiral ureas.

Hao Xu, Stephan J Zuend, Matthew G Woll, Ye Tao, Eric N Jacobsen

Index: Science 327(5968) , 986-90, (2010)

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Abstract

Cationic organic intermediates participate in a wide variety of useful synthetic transformations, but their high reactivity can render selectivity in competing pathways difficult to control. Here, we describe a strategy for inducing enantioselectivity in reactions of protio-iminium ions, wherein a chiral catalyst interacts with the highly reactive intermediate through a network of noncovalent interactions. This interaction leads to an attenuation of the reactivity of the iminium ion and allows high enantioselectivity in cycloadditions with electron-rich alkenes (the Povarov reaction). A detailed experimental and computational analysis of this catalyst system has revealed the precise nature of the catalyst-substrate interactions and the likely basis for enantioinduction.