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Enantioselective Organocatalytic Singly Occupied Molecular Orbital Activation: The Enantioselective α-Enolation of Aldehydes

Jang, Hye-Young and Hong, Jun-Bae and MacMillan, David W. C. (2007) Enantioselective Organocatalytic Singly Occupied Molecular Orbital Activation: The Enantioselective α-Enolation of Aldehydes. Journal of the American Chemical Society, 129 (22). pp. 7004-7005. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170426-080659860

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Abstract

The first enantioselective organocatalytic α-enolation of aldehydes has been accomplished using singly occupied molecular orbital (SOMO) catalysis. Chiral secondary amines react with aldehydes to form transient enamines that undergo selective one-electron oxidation to generate electrophilic radical cations. These SOMO-activated radical cations are susceptible to attack by ketone-derived enol silanes, rendering α-substituted-γ-ketoaldehyde products with uniformly high levels of asymmetric induction. Wide latitude in both the aldehyde and enolsilane component is readily accommodated, allowing generic access to a diverse assortment of enantioenriched 1,4-dicarbonyl compounds. This report highlights the potential of SOMO catalysis to enable the development of entirely new classes of asymmetric reactions that have no traditional catalytic equivalents.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja0719428DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja0719428PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja0719428PublisherSupporting Information
Additional Information:© 2007 American Chemical Society. Received March 19, 2007. Publication Date (Web): May 12, 2007. Financial support was provided by the NIHGMS (Grant R01 GM078201-01-01) and kind gifts from Amgen and Merck. Robert A. Pascal is thanked for his assistance in carrying out DFT calculations.
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Funding AgencyGrant Number
NIHR01 GM078201-01-01
AmgenUNSPECIFIED
MerckUNSPECIFIED
Issue or Number:22
Record Number:CaltechAUTHORS:20170426-080659860
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170426-080659860
Official Citation:Enantioselective Organocatalytic Singly Occupied Molecular Orbital Activation:  The Enantioselective α-Enolation of Aldehydes Hye-Young Jang, Jun-Bae Hong, and David W. C. MacMillan Journal of the American Chemical Society 2007 129 (22), 7004-7005 DOI: 10.1021/ja0719428
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76937
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:26 Apr 2017 15:55
Last Modified:03 Oct 2019 17:51

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