Synthesis, Table of Contents Synthesis 2012; 44(24): 3789-3796DOI: 10.1055/s-0032-1317524 paper © Georg Thieme Verlag Stuttgart · New York Enantioselective Synthesis of Axially Chiral Tetrasubstituted Allenes via Lipase-Catalyzed Desymmetrization Matthias Hammel Department für Chemie, Universität zu Köln, 50939 Cologne, Germany Fax: +49(221)4705102 Email: jan.deska@uni-koeln.de , Jan Deska* Department für Chemie, Universität zu Köln, 50939 Cologne, Germany Fax: +49(221)4705102 Email: jan.deska@uni-koeln.de › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract Lipase from Pseudomonas fluorescens efficiently catalyzes the transesterification of prochiral tetrasubstituted allenic diols yielding highly enantioenriched axially chiral allenyl monoesters. In combination with subsequent 5-endo-trig cyclizations geminally disubstituted dihydrofurans are accessible in high optical purity. Key words Key wordsallenes - axial chirality - desymmetrization - biocatalysis - 5-endo-trig cyclization Full Text References References 1a Koeller KM, Wong C.-H. Nature 2001; 409: 232 1b Faber K. Biotransformations in Organic Chemistry . 5th ed. Springer; Berlin: 2008 1c Gotor V, Alfonso I, García-Urdiales E. Asymmetric Organic Synthesis with Enzymes . Wiley-VCH; Weinheim: 2008 1d Drauz K, Gröger H, May O. Enzyme Catalysis in Organic Synthesis: A Comprehensive Handbook . 3rd ed. Wiley-VCH; Weinheim: 2012 2a Schmid RD, Verger R. Angew. Chem. Int. Ed. 1998; 37: 1608 ; Angew. Chem. 1998, 110, 1694 2b Bornscheuer UT, Kazlauskas RJ. Hydrolases in Organic Synthesis – Regio- and Stereoselective Biotransformations. 2nd ed. Wiley-VCH; Weinheim: 2005 3a Klibanov AM. Nature 2001; 409: 241 3b Reetz MT. Curr. Opin. Chem. Biol. 2002; 6: 145 For examples of non-hydrolase activity by lipases, see: 4a Torre O, Alfonso I, Gotor V. Chem. Commun. 2004; 1724 4b Svedendahl M, Hult K, Berglund P. J. Am. Chem. Soc. 2005; 127: 17988 4c Carlqvist P, Svedendahl M, Branneby C, Hult K, Brinck T, Berglund P. ChemBioChem 2005; 6: 331 4d Li C, Feng X.-W, Wang N, Zhou Y.-J, Yu X.-Q. Green Chem. 2008; 10: 616 5a Ramaswamy S, Hui RA. H. F, Jones JB. J. Chem. Soc., Chem. Commun. 1986; 1545 5b Gil G, Ferre E, Meou A, Le Petit J, Triantaphylides C. Tetrahedron Lett. 1987; 28: 1647 5c Jones BC. N. M, Silverton JV, Simons C, Megati S, Nishimura H, Maeda Y, Mitsuya H, Zemlicka J. J. Med. Chem. 1995; 38: 1397 5d Pietzsch M, Vielhauer O, Pamperin D, Ohse B, Hopf H. J. Mol. Cat. B: Enzym. 1999; 6: 51 5e Cipiciani A, Bellezza F. J. Mol. Cat. B: Enzym. 2002; 17: 261 5f Carballeira JD, Krumlinde P, Bocola M, Vogel A, Reetz MT, Bäckvall J.-E. Chem. Commun. 2007; 1913 5g Deska J, Bäckvall J.-E. Org. Biomol. Chem. 2009; 7: 3379 5h Deska J, del Pozo Ochoa C, Bäckvall J.-E. Chem.–Eur. J. 2010; 16: 4447 6a Manzuna Sapu C, Bäckvall J.-E, Deska J. Angew. Chem. Int. Ed. 2011; 50: 9731 ; Angew. Chem. 2011, 123, 9905 6b For a review on enzyme-catalyzed desymmetrizations, see: García-Urdiales E, Ignacio A, Gotor V. Chem. Rev. 2005; 105: 313 7a Rona P, Crabbé P. J. Am. Chem. Soc. 1969; 91: 3289 7b Zelder C, Krause N. Eur. J. Org. Chem. 2004; 3968 8a Tsuji J, Watanabe H, Minami I, Shimizu I. J. Am. Chem. Soc. 1985; 107: 2196 8b Keinan E, Bosch E. J. Org. Chem. 1986; 51: 4006 8c For a review on palladium-catalyzed allenylation, see also: Tsuji J, Mandai T. Angew. Chem., Int. Ed. Engl. 1996; 34: 2589 9a Modern Allene Chemistry . Krause N, Hashmi AS. K. Wiley-VCH; Weinheim: 2004 9b Ma S. Chem. Rev. 2005; 105: 2829 9c Yu S, Ma S. Angew. Chem. Int. Ed. 2012; 51: 3074 ; Angew. Chem. 2012, 124, 3128 10a Ma S. Acc. Chem. Res. 2003; 36: 701 10b Álvarez-Corral M, Muñoz-Dorado M, Rodríguez-García I. Chem. Rev. 2008; 108: 3174 10c Shen HC. Tetrahedron 2008; 64: 3885 10d Rudolph M, Hashmi AS. K. Chem. Commun. 2011; 47: 6536 For Brønsted acid mediated cycloisomerization of allene carboxylates, see: 11a Musierowicz S, Wróblewski AE. Tetrahedron 1977; 34: 461 11b Krause N, Laux M, Hoffmann-Röder A. Tetrahedron Lett. 2000; 41: 9613 12 Especially the anisyl derivatives 2h and 3h showed high susceptibility to acid-catalyzed cycloisomerization. Obviously, even trace amounts of acid in the NMR solvent seem to favor cyclization as signals of the corresponding dihydrofuran appear as minor impurities in the NMR spectra; see the Supporting Information. 13a Marshall JA, Pinney KG. J. Org. Chem. 1993; 58: 7180 13b Larivée A, Unger JB, Thomas M, Wirtz C, Dubost C, Handa S, Fürstner A. Angew. Chem. Int. Ed. 2011; 50: 304 ; Angew. Chem. 2011, 123, 318 Supplementary Material Supplementary Material Supporting Information
