Synlett, Table of Contents Synlett 2013; 24(12): 1529-1532DOI: 10.1055/s-0033-1338960 letter © Georg Thieme Verlag Stuttgart · New YorkOn a Chemoenzymatic Desymmetrization–Ring Expansion Strategy towards Functionalized N-Heterocycles Daniel Thiel Department für Chemie, Universität zu Köln, Greinstr. 4, 50939 Cologne, Germany Fax: +49(221)4705102 Email: jan.deska@uni-koeln.de , Jan Deska* Department für Chemie, Universität zu Köln, Greinstr. 4, 50939 Cologne, Germany Fax: +49(221)4705102 Email: jan.deska@uni-koeln.de› Author AffiliationsRecommend Article Abstract Buy Article All articles of this category Abstract The direct combination of the desymmetrization of N-heterocyclic meso-diols using lipase from Mucor miehei as biocatalyst and subsequent ring expansion of the optically active products by activation of the remaining hydroxy group gives rise to functionalized nonsymmetrical piperidines in a highly enantio- and diastereoselective manner. Keywords Keywordsdesymmetrization - biocatalysis - ring expansion - heterocycles - azasugars Full Text References References and Notes 1a Beckmann E. Ber. Dtsch. Chem. Ges. 1886; 19: 988 1b Wallach O. Justus Liebigs Ann. Chem. 1900; 312: 171 2 Faworsky A, Boshowski W. J. Russ. Phys. Chem. Soc. 1914; 46: 1097 ; Chem. Zentralbl. 1915, 984 3 For a review, see: Holub N, Blechert S. Chem. Asian J. 2007; 2: 1064 For recent examples in natural product synthesis, see: 4a Larionov OV, Corey EJ. J. Am. Chem. Soc. 2008; 130: 2954 4b Matovic R, Ivkovic A, Manojlovic M, Tokic-Vujosevic Z, Sicic RN. J. Org. Chem. 2006; 71: 9411 5a Cossy J, Dumas C, Michel P, Gomez Pardo D. Tetrahedron Lett. 1995; 36: 549 5b Cossy J, Dumas C, Gomez Pardo D. Synlett 1997; 905 5c Déchamps I, Gomez Pardo D, Cossy J. ARKIVOC 1997; (v): 38 5d Cossy J, Dumas C, Gomez Pardo D. Eur. J. Org. Chem. 1999; 1693 6a Déchamps I, Gomez Pardo D, Cossy J. Eur. J. Org. Chem. 2007; 4224 6b Cochi A, Gomez Pardo D, Cossy J. Eur. J. Org. Chem. 2012; 2023 7 For a review, see: García-Urdiales E, Alfonso I, Gotor V. Chem. Rev. 2011; 111: PR110 Selected examples: 8a Chênevert R, Dickman M. J. Org. Chem. 1996; 61: 3332 8b Lesma G, Colombo A, Landoni N, Sacchetti A, Silvani A. Tetrahedron: Asymmetry 2007; 18: 1948 8c Donohoe TJ, Rigby CL, Thomas RE, Nieuwenhuys WF, Bhatti FL, Cowley AR, Bhalay G, Linney ID. J. Org. Chem. 2006; 71: 6298 8d Chênevert R, Jacques F, Giguère P, Dasser M. Tetrahedron: Asymmetry 2008; 19: 1333 8e Donohoe TJ, Thomas RE, Cheeseman MD, Rigby CL, Bhalay G, Linney ID. Org. Lett. 2008; 10: 3615 9 Kawanami et al. described the enzymatic kinetic resolution of corresponding trans-2,5-disubstituted pyrrolidines: Kawanami Y, Moriya H, Goto Y, Tsukao K, Hashimoto M. Tetrahedron 1996; 52: 565 Literature based on our recent studies on lipase-catalyzed transformations of primary alcohols: 10a Deska J, Bäckvall J.-E. Org. Biomol. Chem. 2009; 7: 3379 10b Manzuna Sapu C, Bäckvall J.-E, Deska J. Angew. Chem. Int. Ed. 2011; 50: 9731 ; Angew. Chem. 2011, 123, 9905 10c Hammel M, Deska J. Synthesis 2012; 44: 3789 11 Formation of undesired trans-diastereomers was not observed, neither for diols 1 and 3 nor for diacetates 4 and 5. 12 Unfortunately, this protocol proved to be not suitable for the ring expansion of unsaturated monoacetate 2c, as decomposition was observed under these conditions. 13 Jarvis SB. D, Charette AB. Org. Lett. 2011; 13: 3830 14 Yasuda K, Kizu H, Yamashita T, Kameda Y, Kato A, Nash RJ, Fleet GW. J, Molyneux RJ, Asano N. J. Nat. Prod. 2002; 65: 198 Supplementary Material Supplementary Material Supporting Information
