Synlett 2010(13): 2041-2044  
DOI: 10.1055/s-0030-1258540
CLUSTER
© Georg Thieme Verlag Stuttgart ˙ New York

Asymmetric CuH-Catalyzed 1,4-Reductions in Water at Room Temperature

Shenlin Huang, Karl R. Voigtritter, John B. Unger, Bruce H. Lipshutz*
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA
Fax: +1(805)8938265; e-Mail: lipshutz@chem.ucsb.edu;
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Publikationsverlauf

Received 18 June 2010
Publikationsdatum:
02. August 2010 (online)

Abstract

Taking advantage of micellar catalysis in water, asymmetric hydrosilylation reactions can now be conducted at ambient temperatures using water, and only water, as the global medium.

    References and Notes

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  • General Procedure for a CuH-Catalyzed Asymmetric 1,4-Reduction in Water To a 5 mL glass vial was added Cu(OAc)2˙H2O (3 mg, 0.015 mmol) and (R)-3,5-Xyl-MeO-BIPHEP (10.4 mg, 0.015 mmol). After an atmosphere exchange with argon, 2 wt% TPGS-750-M/H2O (2 mL) was added, and the mixture was vigorously stirred for 2 h. Isophorone (75 µL, 0.5 mmol) was added and the reaction continued with stirring for 10 min. PMHS (0.3 mL) was added dropwise to the reaction over 6 h. The reaction was stirred vigorously overnight (12 h), then quenched with sat. aq NH4F (0.3 mL) and stirred for an additional 2 h. The resulting solution was filtered through a short plug of silica gel and concentrated under vacuum. The product was purified via silica gel flash chromatography (10% Et2O-hexanes) to afford the desired 3,3,5-trimethyl-cyclohexanone as a colorless oil (62 mg, 88%). The ee was determined by chiral GC on a β-DEX SM column, 100 ˚C isotherm, 1 mL/min; racemic t R = 13.67 and 14.81 min; nonracemic t R = 13.65 (minor) and 14.85 (major), 94% ee. The product spectral data matched those previously reported:
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12

Lipshutz, B. H.; Ghorai, S. University of California, Santa Barbara, CA, in preparation. TPGS-750-M = polyoxyethanyl-α-tocopheryl succinate.