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

Hye-Young Jang,† Jun-Bae Hong, and David W. C. MacMillan*
Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, and Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125
J. Am. Chem. Soc., 2007, 129 (22), pp 7004–7005
DOI: 10.1021/ja0719428
Publication Date (Web): May 12, 2007
Copyright © 2007 American Chemical Society
†

 Ajou University, Suwon, Korea.

,
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, dmacmill@princeton.edu

Abstract

Abstract Image

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.

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History

  • Published In Issue June 06, 2007
  • Received March 19, 2007

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