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.
Key words
copper hydride - hydrosilylations - reduction - asymmetric catalysis - micellar catalysis - green
chemistry
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 ˙H2 O
(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/H2 O (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 NH4 F (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% Et2 O-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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