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Originally published in Science Express on 29 March 2007
Science 27 April 2007:
Vol. 316. no. 5824, pp. 582 - 585
DOI: 10.1126/science. 1142696
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Reports

Enantioselective Organocatalysis Using SOMO Activation

Teresa D. Beeson,1,2 Anthony Mastracchio,1,2 Jun-Bae Hong,1,2 Kate Ashton,1,2 David W. C. MacMillan1,2*

The asymmetric {alpha}-addition of relatively nonpolar hydrocarbon substrates, such as allyl and aryl groups, to aldehydes and ketones remains a largely unsolved problem in organic synthesis, despite the wide potential utility of direct routes to such products. We reasoned that well-established chiral amine catalysis, which activates aldehydes toward electrophile addition by enamine formation, could be expanded to this important reaction class by applying a single-electron oxidant to create a transient radical species from the enamine. We demonstrated the concept of singly occupied molecular orbital (SOMO) activation with a highly selective {alpha}-allylation of aldehydes, and we here present preliminary results for enantioselective heteroarylations and cyclization/halogenation cascades.

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

* To whom correspondence should be addressed. E-mail: dmacmill{at}princeton.edu

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