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. doi:10.1021/ja0719428. 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 | ||||||||||||
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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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Issue or Number: | 22 | ||||||||||||
DOI: | 10.1021/ja0719428 | ||||||||||||
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: | 15 Nov 2021 17:04 |
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