A practical method for optical resolution of racemic alcohols or esters via lipase-catalyzed transformation and sulfation

Chemistry Letters

Volumn , Issue 5, 2000, Pages 448-449

  Yamano, Toru ^a   Kikumoto, Fumio ^a   Yamamoto, Shozo ^a   Miwa, Katsuhiko ^a   Kawada, Mitsuru ^a   Ito, Tatsuya ^a   Ikemoto, Tomomi ^a   Tomimatsu, Kiminori ^a   Mizuno, Yukio ^a  

^a TAKEDA PHARMACEUTICAL COMPANY LIMITED   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0034354383     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.2000.448     Document Type: Article

References (14)

1. a) "Enzymatic Reactions in Organic Media," ed by A. M. P. Koskinen and A. M. Klibanov, Blackie Academic & Professional, Glasgow (1996).
2. b) "Hydrolases in Organic Synthesis," ed by U. T. Bornscheuer and R. J. Kazlauskas, Wiley-VCH, Weinheim (1999).
3. a) Y. Terao, K. Tsuji, M. Murata, K. Achiwa, T. Nishio, N. Watanabe, and K. Seto, Chem. Pharm. Bull., 37, 1653 (1989).
4. b) A. L. Gutman, D. Bernner, and A. Boltanski, Tetrahedron: Asymmetry, 4. 839 (1993).
5. Preparation of (+)-methyl 2-acetyloxy-2-phenylacetate and (-)-methyl 2-hydroxy-2-phenylacetate was performed as follows: A suspension of lipase (LIP, Toyobo Co. Ltd.) 1.50 g, (±)-methyl 2-hydroxy-2-phenylacetate 1.00 g, Molecular sieves 4A 5.0 g, and vinyl acetate 3.0 ml in diisopropyl ether 100 ml was stirred at 35 °C for 3 h. After the lipase was removed by filtration, the filtrate was concentrated under reduced pressure to give a residue containing methyl (S)-(+)-2-(acetyloxy)-2-phenylacetate (93% ee) and methyl (R)-(-)-2-hydroxy-2-phenylacetate (99% ee). The residue was dissolved in pyridine 10 ml and DMF 2 ml, and to this solution sulfur trioxide pyridine complex 1.95 g was added. After stirring at room temperature for 1 h, diisopropyl ether 70 ml was added. The mixture was washed with successive water, dilute hydrochloric acid and brine, then dried over sodium sulfate. The filtrate was concentrated under reduced pressure to afford methyl (S)-(+)-2-(acetyloxy)-2-phenylacetate 0.559 g (45%, 92% ee) as an oil. The combined aqueous layers were concentrated and treated with 10% methanolic hydrochloric acid. A similar work up afforded methyl (R)-(-)-2-hydroxy-2-phenylacetate 0.341 g (34%, 96% ee).
6. The acetate was hydrolyzed to give an alcohol, which was subjected to HPLC analysis. Column: CHIRALCEL OD (Daicel Chemical Industries, Ltd.), Mobile phase: hexane/2-propanol (97/3), Flow rate: 1.0 ml/min, Detection: UV (280 nm), Temperature: room temperature.
7. Column: CHIRALCEL OD (Daicel Chemical Industries Ltd.), Mobile phase: hexane/2-propanol (99/1), Flow rate: 1.2 ml/min. Detection: UV (254 nm), Temperature: room temperature.
8. Column: CHIRALCEL OJ (Daicel Chemical Industries, Ltd.), Mobile phase: hexane/2-propanol (98/2), Flow rate: 1.2 ml/min, Detection: UV (220 nm), Temperature: room temperature.
9. Column: CHIRALCEL OB (Daicel Chemical Industries, Ltd.), Mobile phase: hexane/2-propanol (1000/5), Flow rate: 1.0 ml/min. Detection: UV (254 nm), Temperature: room temperature.
10. Column: CHIRALCEL OD two pieces (Daicel Chemical Industries, Ltd.), Mobile phase: hexane/2-propanol (1000/5), Flow rate: 1.0 ml/min, Detection: UV (254 nm), Temperature: room temperature.
11. (GLC) Column: Chirasil Dex-CB (25 m × 0.25 mm I.D., Chrompack), Oven temperature: 80 °C ∼ 150 °C, Injection temperature: 200 °C, Detection temperature: 200 °C, Carrier gas: Helium.
12. Y. Hirose, Y. Imada, Y. Yamashita, M. Kamori, H. Ozaki, and J. Takahashi, presented at 9th International Symposium on Chiral Discrimination, Nagoya, 1997, Abstr., PP1-46, p.67.
13. M.-J. Kim and Y. K. Choi, J.Org.Chem., 57, 1605 (1992).
14. T. Ohtani, H. Nakatsukasa, M. Kamezawa, H. Tachibana, and Y. Naoshima, J. Mol. Catal. B: Enzymatic, 4, 53 (1998).