Enantioselective Reductive Coupling of Acetylene to N-Arylsulfonyl Imines via Rhodium Catalyzed C−C Bond-Forming Hydrogenation:  (Z)-Dienyl Allylic Amines

Eduardas Skucas, Jong Rock Kong, and Michael J. Krische*
University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712
J. Am. Chem. Soc., 2007, 129 (23), pp 7242–7243
DOI: 10.1021/ja0715896
Publication Date (Web): May 19, 2007
Copyright © 2007 American Chemical Society
*

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

, mkrische@mail.utexas.edu

Abstract

Abstract Image

The first highly enantioselective catalytic vinylation of aldimines to furnish allylic amines is reported. Exposure of aromatic and aliphatic N-arylsulfonyl aldimines 1a−12a to equal volumes of acetylene and hydrogen gas at 45 °C and ambient pressure in the presence of chirally modified cationic rhodium catalysts provides the (Z)-dienyl allylic amines 1b−12b in highly optically enriched form (93−98% ee) and as single geometrical isomers (>95:5, Z/E). The coupling products 1b−12b arise via multicomponent coupling of four molecules:  two molecules of acetylene, a molecule of aldimine, and elemental hydrogen. Unlike other imine additions involving nonstabilized carbanions, the present protocol circumvents use of preformed organometallic reagents.

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History

  • Published In Issue June 13, 2007
  • Received March 6, 2007

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