Biocatalysis in Ionic Liquids: Markedly Enhanced Enantioselectivity of Lipase

Organic Letters

Volumn 3, Issue 10, 2001, Pages 1507-1509

  Kim, Kwang Wook ^a   Song, Boyoung ^a   Choi, Min Young ^a   Kim, Mahn Joo ^a  

^a Pohang University of Science and Technology (POSTECH)   (South Korea)

Author keywords

[No Author keywords available]

Indexed keywords

ION; SOLVENT; TRIACYLGLYCEROL LIPASE;

ARTICLE; BURKHOLDERIA CEPACIA; CANDIDA; CATALYSIS; DRUG EFFECT; ENZYMOLOGY; METABOLISM; STEREOISOMERISM;

BURKHOLDERIA CEPACIA; CANDIDA; CATALYSIS; IONS; LIPASE; SOLVENTS; STEREOISOMERISM;

EID: 0035902269     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol015824f     Document Type: Article

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24. During the preparation of this manuscript, a report describing the improved enantioselectivity of lipase in ionic liquids has appeared (Schoefer, S. H.; Kaftzik, N.; Wasserscheid, P.; Kragl, U. Chem. Commun. 2001, 425).
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32. Experimental detail: 3d (109 mg, 0.6 mmol), vinyl acetate (1.8 mmol), and PCL (218 mg) were mixed with ionic liquid 2 (3 mL), and the resulting heterogeneous mixture was stirred at 25°C. When the reaction reached slightly over 50% completion (48 h), the reaction mixture was extracted with ethyl ether (5 times with a 20 mL portion). The ethereal phase was concentrated and subjected to silica gel chromatography to provide the unreacted substrates ((R)-3d, 47.3 mg, 0.26 mmol, 43%, >99.5% ee) and the acetylated products ((S)-4d. 63 mg, 0.28 mmol, 47%, 97.7% ee). The second reaction was performed under the same conditions, except that the reaction was carried to about 46% completion (36 h), to afford the unreacted substrates (46.5 mg, 0.256 mmol, 43%, 85.8% ee) and the acetylated product (56.9 mg, 0.255 mmol, 42%, >99.5% ee). The optical purities were determined by HPLC using a chiral column. See the footnote in Table 1 for the HPLC conditions.
33. The activities of lipases decreased roughly in the following orders: toluene > THF≈ 1 ≈ 2 for the reaction of 3a, toluene > THF ≈ 1 > 2 for the reaction of 3b, toluene > THF ≈ 1 >> 2 for the reaction of 3c, and toluene ≈ THF ≈ 2 > 1 for the reaction of 3d. (13) From Solvent Innovation GMBH, Cologne. The prices of 1 and 2 are, respectively, 529.30 and 647.50 DM for 100 mL. In this work, we used chemically prepared ionic liquids. See ref 7.
34. When the reaction corresponding to entry 4 in Table 1 was scaled up by 10-fold (3a, 225 mg. 1.5 mmol), the same level of enantioselectivity was realized.
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