Enantioselective Iridium-Catalyzed Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level Using Allyl Acetate as an Allyl Metal Surrogate

In Su Kim, Ming-Yu Ngai and Michael J. Krische
University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712
J. Am. Chem. Soc., 2008, 130 (20), pp 6340–6341
DOI: 10.1021/ja802001b
Publication Date (Web): April 29, 2008
Copyright © 2008 American Chemical Society

Abstract

Abstract Image

Protocols for highly enantioselective carbonyl allylation from the alcohol or aldehyde oxidation level are described based upon transfer hydrogenative C−C coupling. Exposure of allyl acetate to benzylic alcohols 1a−i in the presence of an iridium catalyst derived from [IrCl(cod)]2 and (R)-BINAP delivers products of C-allylation 2a−i. Employing isopropanol as terminal reductant, exposure of allyl acetate to aryl aldehydes 3a−i in the presence of an iridium catalyst derived from [IrCl(cod)]2 and (−)-TMBTP delivers identical products of C-allylation 2a−i. In all cases examined, exception levels of enantioselectivity are observed. Thus, enantioselective carbonyl allylation is achieved from the alcohol or aldehyde oxidation level in the absence of any preformed allylmetal reagents. These studies define a departure from preformed organometallic reagents in carbonyl additions that transcend the boundaries of oxidation level.

View: Full Text HTML | Hi-Res PDF | PDF w/ Links

Tools

History

  • Published In Issue May 21, 2008
  • Article ASAPApril 29, 2008
  • Received: March 18, 2008

Recommend & Share

Related Content

Other ACS content by these authors: