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

Reports

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 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. Here we demonstrate the concept of singly occupied molecular orbital (SOMO) activation with a highly selective {alpha}-allylation of aldehydes, and also present preliminary results for enantioselective heteroarylations and cyclization/halogenation cascades.


THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
Merging Photoredox Catalysis with Organocatalysis: The Direct Asymmetric Alkylation of Aldehydes.
D. A. Nicewicz and D. W. C. MacMillan (2008)
Science 322, 77-80
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Science. ISSN 0036-8075 (print), 1095-9203 (online)