Job/Unit: O42019
/KAP1
Date: 16-04-14 10:47:07
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Catalyzed Asymmetric α-Hydroxylation of β-Dicarbonyl Compounds
Chem. 2012, 124, 1266–1269; d) L. Y. Liu, Y. N. Zhu, K. M.
General Procedure for the Synthesis of Catalysts L2–L10: A mixture
of lappaconine (1.00 g, 34.2 mmol), benzaldehyde dimethyl acetal
(3.0 equiv.), p-toluenesulfonic acid (PTSA; 2.0 equiv.) and toluene
(50 mL) was heated to reflux in a 50 mL round-bottomed flask
with a Dean–Stark apparatus overnight. The solvent was removed
in vacuo, and the crude mixture was dissolved in CH2Cl2 (100 mL).
The solution was washed with saturated Na2CO3 (3ϫ 20 mL),
water (3ϫ 20 mL), brine (3ϫ 20 mL) and dried with Na2SO4. The
solvent was removed in vacuo to give the crude product. The crude
product was purified by column chromatography on silica gel (pe-
troleum ether/EtOAc/TEA, 80:20:2 to 50:50:2) to give the corre-
sponding catalyst.
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General Procedure for Enantioselective Hydroxylation: β-Oxo ester
1 (0.1 mmol) and catalyst (10 mol-%) were added to a test tube
equipped with a stirring bar and dissolved in CHCl3/MeOH (9:1,
2 mL). 30% H2O2 (0.5 mmol, 50 μL) was added, and the resulting
mixture was stirred at 15 °C. After completion of the reaction, the
reaction mixture was concentrated in vacuo. The residue was puri-
fied by flash chromatography to give alcohols 2. The ee of the prod-
uct was determined by chiral HPLC.
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Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures, characterization of the prepared
compounds, copies of NMR spectra, and chiral HPLC data of the
hydroxylation products.
Acknowledgments
We would likely to thank the National Natural Science Foundation
of China (No. 21176041) and the State Key Laboratory of Fine
Chemicals for their support.
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Received: February 5, 2014
Published Online:
Eur. J. Org. Chem. 0000, 0–0
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