Enantioselective Organocatalysis Using SOMO Activation

doi:10.1126/science. 1142696

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Published Online March 29, 2007
Science DOI: 10.1126/science. 1142696

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Submitted on February 20, 2006
Accepted on March 20, 2007

Enantioselective Organocatalysis Using SOMO Activation

Teresa D. Beeson ¹, Anthony Mastracchio ¹, Jun-Bae Hong ¹, Kate Ashton ¹, David W. C. MacMillan ¹^*

¹ Merck Center for Catalysis, Department of Chemistry, Princeton University, Princeton, NJ 08544, USA; Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.

^* To whom correspondence should be addressed.
David W. C. MacMillan , E-mail: dmacmill{at}princeton.edu

The asymmetric ${alpha}$ -addition of relatively non-polar hydrocarbonsubstrates, such as allyl and aryl groups, to aldehydes andketones remains a largely unsolved problem in organic synthesis,despite the wide potential utility of direct routes to suchproducts. We reasoned that well-established chiral amine catalysis,which activates aldehydes toward electrophile addition by enamineformation, could be expanded to this important reaction classby applying a single-electron oxidant to create a transientradical species from the enamine. Here we demonstrate the conceptof singly occupied molecular orbital (SOMO) activation witha highly selective ${alpha}$ -allylation of aldehydes, and also presentpreliminary results for enantioselective heteroarylations andcyclization/halogenation cascades.