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

 

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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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Unpublished results (E. Genin, D.E.A. Multinational de Chimie Moléculaire de l’Ecole Polytechnique).

Ethylene glycol, purchased from Acros, contains 0.05% water and was used without further treatment.

Typical procedure : A solution of Rh(acac)(C₂H₄)₂ (1.3 mg, 0.006 mmol) and (R)-Digm-BINAP (5.0 mg, 0.006 mmol) in degassed ethyleneglycol (1.0 mL) was stirred under argon for 15 minutes at room temperature, then phenylboronic acid (122 mg, 1 mmol), sodium carbonate (43 mg, 0.4 mmol) and cyclohexenone (20 µL, 0.2 mmol) were successively added. The heterogeneous mixture was stirred at 100 °C until completion of the reaction (gas chromatography). After cooling at room temperature the solution was extracted two times with ethyl acetate. The combined organic layers were filtered on a short pad of silica gel and evaporated under reduced pressure. A slight yellow oil (34 mg, 100%) was obtained. The purity of the compound was checked by gas chromatography and ¹H NMR. The enantiomeric excess was determined by HPLC (Daicel Chiralcel OD-H, hexane/i-PrOH = 98:2, 1 mL/min).