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Synfacts 2007(6): 0649-0649
DOI: 10.1055/s-2007-968564
DOI: 10.1055/s-2007-968564
Organo- and Biocatalysis
© Georg Thieme Verlag Stuttgart · New York
Enantioselective Organocatalysis Using SOMO Activation
T. D. Beeson, A. Mastracchio, J.-B. Hong, K. Ashton, D. W. C. Macmillan*
Princeton University and California Institute of Technology, Pasadena, USA
Further Information
Publication History
Publication Date:
22 May 2007 (online)
![](https://www.thieme-connect.de/media/synfacts/200706/lookinside/thumbnails/10.1055-s-2007-968564-1.jpg)
Significance
The authors report a direct enantioselective allylic alkylation of aldehydes using SOMO activation. They recognized that a one-electron oxidation of a transient enamine species would generate a 3π-electron radical cation with a singly occupied molecular orbital (SOMO) that is activated to a variety of π-rich nucleophiles. Imidazolidinium salt 1 was found to be the best catalyst and ceric ammonium nitrate (CAN) was used as the stoichiometric oxidant for the allylic alkylation of different aldehydes. With 20 mol% of the catalyst 1 and two equivalents of CAN, good to high yields (72-88%) and high enantioselectivities (ee = 93:7 to 98:2) are obtained for a variety of allylsilanes.