Title: Enzymatic Resolution of Alcohols Coupled with Ruthenium‐Catalyzed Racemization of the Substrate Alcohol
Abstract: Angewandte Chemie International Edition in EnglishVolume 36, Issue 11 p. 1211-1212 Communication Enzymatic Resolution of Alcohols Coupled with Ruthenium-Catalyzed Racemization of the Substrate Alcohol†‡ Anna L. E. Larsson, Anna L. E. Larsson Department of Organic Chemistry, Uppsala University, Box 531, S-75121 Uppsala (sweden), Fax: Int. code +(81)-508-542, e-mail: [email protected]Search for more papers by this authorB. Anders Persson, B. Anders Persson Department of Organic Chemistry, Uppsala University, Box 531, S-75121 Uppsala (sweden), Fax: Int. code +(81)-508-542, e-mail: [email protected]Search for more papers by this authorProf. Jan-E. Bäckvall, Corresponding Author Prof. Jan-E. Bäckvall Department of Organic Chemistry, Uppsala University, Box 531, S-75121 Uppsala (sweden), Fax: Int. code +(81)-508-542, e-mail: [email protected]Department of Organic Chemistry, Uppsala University, Box 531, S-75121 Uppsala (sweden), Fax: Int. code +(81)-508-542, e-mail: [email protected]Search for more papers by this author Anna L. E. Larsson, Anna L. E. Larsson Department of Organic Chemistry, Uppsala University, Box 531, S-75121 Uppsala (sweden), Fax: Int. code +(81)-508-542, e-mail: [email protected]Search for more papers by this authorB. Anders Persson, B. Anders Persson Department of Organic Chemistry, Uppsala University, Box 531, S-75121 Uppsala (sweden), Fax: Int. code +(81)-508-542, e-mail: [email protected]Search for more papers by this authorProf. Jan-E. Bäckvall, Corresponding Author Prof. Jan-E. Bäckvall Department of Organic Chemistry, Uppsala University, Box 531, S-75121 Uppsala (sweden), Fax: Int. code +(81)-508-542, e-mail: [email protected]Department of Organic Chemistry, Uppsala University, Box 531, S-75121 Uppsala (sweden), Fax: Int. code +(81)-508-542, e-mail: [email protected]Search for more papers by this author First published: June 16, 1997 https://doi.org/10.1002/anie.199712111Citations: 302 † We would like to thank Dr. Ratan, L. Chowdhury who performed the initial studies on the racemization of alcohols. Candida antarctica component B Lipase (Novozym 435) was a gift from Novo Nordisk A/S, Denmark, Financial support by the Swedish National Science Research Council is gratefully acknowledged. ‡ Dedicated to Professor Henri B. Kagan AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract A specifically designed acyl donor, an efficient enzyme, and a stable and reliable ruthenium catalyst are fundamental for the resolution of the racemic alcohols described here (see scheme on the right). For R1 Ph and R2 Me, 100% conversion into the corresponding acetate was achieved with greater than 99.5% ee. References 1(a) A. M. Kilbanov, Acc. Chem. Res. 1990, 23, 114; (b) M. Ohno, M. Otsaka, Org. React. 1990, 37, 1; (c) K. 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OMCOS 7 1993, Kobe, Japan, p. 68. 11 J. P. Genêt, V. Ratovelomanana-Vidal, C. Pinel, Synlett. 1993 478. 12(a) H. E. Schink, J. E. Bäckvall, J. Org. Chem. 1992, 57, 1588. Correction: J. Org. Chem. 1992, 57, 6082. (b) J. E. Bäckvall, R. Gatti, H. E. Schink, Synthesis 1993 343; (c) R. P. G. Gatti, A. L. E. Larsson, and J. E. Bäckvall, J. Chem. Soc. Perkin Trans. 1, 1997, 577. 13 E. L. Eliel, S. H. Wilen, L. N. Mander, Stereochemistry of Organic Compounds, Wiley-Interscience, New York, 1994, pp. 315. 14 Starting from (±)-cis-2-methylcyclohexanol a cis/trans ratio of 46:54 was obtained in 14 h at 80 °C with 2 mol% 1, 10 mol% NaOH, and 1 equiv of 2-methylcyclohexanone in 2mL of tBuOH. 15This catalyst is readily prepared from [Ru3CO12] and tetraphenyleyclopentadienone: Y. Shvo, N. Menashe, Organometallics 1991, 10, 3885. 16(a) C. R. Johnson, H. Sakaguchi, Synlett 1992, 813 (b) C. Orrenius, A. Mattson, T. Norin, N. Öhrner, K. Hult, Tetrahedron Asymmetry 1994, 5, 1363; (c) C. Orrenius, N. Öhrner, D. Rotticci, A. Mattson, K. Hult, T. Norin, Tetrahedron Asymmetry 1995, 6, 1217; (d) A. Mattson, C. Orrenius, N. Öhrner, C. R. Unelius, K. Hult, T. Norin, Acta Chem. Scand. 1996, 50, 918; (e) C. R. Johnson, S. J. Bis, Tetrahedron Lett. 1992, 33, 7287; (f) M. Arroyo, J. V. Sinisterra, J. Org. Chem. 1994, 59, 4410; (g) H. Sundram, A. Golebiowski, C. R. Johnson, Tetrahedron Lett. 1994, 35, 6975; (h) M. Pozo, R. Pulido, V. Gotor, Tetrahedron 1992, 48, 6477. 17 In this process the acetaldehyde is reduced to ethanol, which is rapidly acylated, and the process becomes irreversible. Citing Literature Volume36, Issue11June 16, 1997Pages 1211-1212 ReferencesRelatedInformation