Synlett 2002(11): 1791-1794
DOI: 10.1055/s-2002-34861
LETTER
© Georg Thieme Verlag Stuttgart · New York

A New and Practical Procedure for Asymmetric 1,4-Addition of Boronic Acids to α,β-Unsaturated Ketones Catalyzed by Rh-(R)-Digm-BINAP System

Rémi Amengual, Véronique Michelet*, Jean-Pierre Genêt*
Laboratoire de Synthèse Organique, E.N.S.C.P., UMR7573 11 rue P. et M. Curie, 75231 Paris Cedex 05, France
e-Mail: genet@ext.jussieu.fr; e-Mail: michelet@ext.jussieu.fr;
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Publication History

Received 12 July 2002
Publication Date:
21 October 2002 (online)

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Abstract

Rh-catalyzed C-C bond asymmetric formation under basic conditions in organoaqueous or alcoholic solvents has been described using the atropoisomeric water-soluble ligand (R)-Digm-BINAP. The addition of phenylboronic acid to cyclohexenone has been efficiently optimized leading to quantitative yield and enantio­meric excesses up to 98% using 1-3 mol% catalyst. Easy product-catalyst separation has been found using ethylene glycol as the reaction solvent. Other α,β-unsaturated ketones and boronic acids could be engaged in the 1,4-addition. The mole fraction of the catalyst could be decreased to 0.005% with still acceptable ee. A TON of 13200 was obtained.

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