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Enantioselective Organocatalysis Using SOMO Activation

Beeson, Teresa D. and Mastracchio, Anthony and Hong, Jun-Bae and Ashton, Kate and MacMillan, David W. C. (2007) Enantioselective Organocatalysis Using SOMO Activation. Science, 316 (5824). pp. 582-585. ISSN 0036-8075. https://resolver.caltech.edu/CaltechAUTHORS:20141119-144913051

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Abstract

The asymmetric α-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 α-allylation of aldehydes, and we here present preliminary results for enantioselective heteroarylations and cyclization/halogenation cascades.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1126/science. 1142696 DOIArticle
http://www.sciencemag.org/content/316/5824/582PublisherArticle
http://www.sciencemag.org/content/316/5824/582/suppl/DC1PublisherSupporting Information
Additional Information:© 2007 American Association for the Advancement of Science. 20 February 2007; Accepted 20 March 2007; Published online 29 March 2007. We thank R. A. Pascal for invaluable assistance in performing Gaussian DFT calculations and M. Amatore for a late-stage experimental contribution. Financial support was provided by NIH National Institute of General Medical Sciences (grant R01 GM078201-01-01) and by gifts from Amgen, Merck Research Laboratories, and the Astellas Foundation USA. T.D.B. is grateful for a Novartis predoctoral fellowship, J.-B.H. is grateful for a KRF postdoctoral fellowship, and K.A. is grateful for a Merck overseas postdoctoral fellowship.
Funders:
Funding AgencyGrant Number
National Institute of General Medical SciencesR01 GM078201-01-01
AmgenUNSPECIFIED
Merck Research LaboratoriesUNSPECIFIED
Astellas Foundation USAUNSPECIFIED
Novartis predoctoral fellowshipUNSPECIFIED
KRF postdoctoral fellowshipUNSPECIFIED
Merck overseas postdoctoral fellowshipUNSPECIFIED
Issue or Number:5824
Record Number:CaltechAUTHORS:20141119-144913051
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20141119-144913051
Official Citation:Beeson, T. D., Mastracchio, A., Hong, J.-B., Ashton, K., & MacMillan, D. W. C. (2007). Enantioselective Organocatalysis Using SOMO Activation. Science, 316(5824), 582-585. doi: 10.1126/science. 1142696
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:51977
Collection:CaltechAUTHORS
Deposited By: Joanne McCole
Deposited On:19 Nov 2014 23:09
Last Modified:03 Oct 2019 07:38

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