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

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...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2007-06, Vol.129 (22), p.7004-7005
Main Authors: Jang, Hye-Young, Hong, Jun-Bae, MacMillan, David W. C
Format: Article
Language:English
Subjects:
Aldehydes - chemistry
Allyl Compounds - chemistry
Catalysis
Cyclization
Ketones - chemical synthesis
Ketones - chemistry
Models, Molecular
Silanes - chemistry
Stereoisomerism
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Summary: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.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0719428