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http://dx.doi.org/10.14478/ace.2016.1068

Synthesis of Highly Enantiomerically Enriched Arenesulfonic Acid 2-Hydroxy Esters via Kinetic Resolution of Terminal Epoxides  

Lee, Yae Won (Department of Chemical Engineering, Inha University)
Yang, Hee Chun (Department of Chemical Engineering, Inha University)
Kim, Geon-Joong (Department of Chemical Engineering, Inha University)
Publication Information
Applied Chemistry for Engineering / v.27, no.5, 2016 , pp. 490-494 More about this Journal
Abstract
This paper describes the very efficient and highly enantioselective ring opening of terminal epoxides with alkyl and arene sulfonic acid. The dinuclear chiral (salen) Co complexes bearing Lewis acids of Al, Ga and In catalyze the reaction enantioselectively in the presence of tetrabutylammonium chloride using tert-butyl methyl ether as a solvent. The variation of the anion of the tetra butyl ammonium salt has significant impact on the reactivity and selectivity of the asymmetric ring opening of phenyl glycidyl ether with p-toluenesulfonic acid. The order of reactivity and selectivity was found to be $Cl^-$ > $l^-$ > $Br^-$ > $OH^-$. Strong synergistic effects of the different Lewis acid centers of Co-Al, Co-Ga and Co-In complexes were observed in the catalytic process. The dinuclear chiral salen catalyst containing $AlCl_3$ was found to be most active and highly enantioselective (91% ee).
Keywords
enantioselective catalysis; chiral heterometallic salen catalyst; terminal epoxides; sulfonic acids;
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1 L. E. Martinez, J. L. Leighton, D. H. Carsten, and E. N. Jacobsen, Highly enantioselective ring opening of epoxides catalyzed by (salen)Cr(III) complexes, J. Am. Chem. Soc., 117, 5897-5898 (1995).   DOI
2 M. Tokunaga, J. F. Larrow, F. Kakiuchi, and E. N. Jacobsen, Asymmetric catalysis with water: Efficient kinetic resolution of terminal epoxides by means of catalytic hydrolysis, Science, 277, 936-938 (1997).   DOI
3 E. N. Jacobsen, F. Kakiuchi, R. G. Konsler, J. F. Larrow, and M. Tokunaga, Enantioselective catalytic ring opening of epoxides with carboxylic acids, Tetrahedron Lett., 38, 773-776 (1997).   DOI
4 M. Wu and E. N. Jacobsen, Asymmetric ring opening of meso epoxides with thiols: Enantiomeric enrichment using a bifunctional nucleophile, J. Org. Chem., 63, 5252-5254 (1998).   DOI
5 J. M. Ready and E. N. Jacobsen, Asymmetric catalytic synthesis of ${\gamma}$-aryloxy alcohols: Kinetic resolution of terminal epoxides via highly enantioselective ring-opening with phenols, J. Am. Chem. Soc., 121, 6086-6087 (1999).   DOI
6 F. Larrow and E. N. Jacobsen, Asymmetric processes catalyzed by chiral (Salen) metal complexes, Top. Organomet. Chem., 6, 123-152 (2004).
7 G. Bartoli, M. Bosco, A. Carlone, M. Locatelli, P. Melchiorre, and L. Sambri, Asymmetric catalytic synthesis of enantiopure N-protected 1,2-amino alcohols, Org. Lett., 6, 3973-3975 (2004).   DOI
8 G. Bartoli, M. Bosco, A. Carlone, M. Locatelli, P. Melchiorre, and L. Sambri, Asymmetric aminolysis of aromatic epoxides: A facile catalytic enantioselective synthesis of anti-${\beta}$-amino alcohols, Org. Lett., 6, 2173-2176 (2004).   DOI
9 C. K. Shin, S. J. Kim, and G.-J. Kim, New chiral cobalt salen complexes containing Lewis acid BF3; A highly reactive and enantioselective catalyst for the hydrolytic kinetic resolution of epoxides, Tetrahedron Lett., 45, 7429-7433 (2004).   DOI
10 S. S. Thakur, W. Li, S. J. Kim, and G.-J. Kim, Highly reactive and enantioselective kinetic resolution of terminal epoxides with $H_2O$ and HCl catalyzed by new chiral (salen) Co complex linked with Al, Tetrahedron Lett., 46, 2263-2266 (2005).   DOI
11 W. Li, S. S. Thakur, S.-W. Chen, C. K. Shin, R. B. Kawthekar, and G.-J. Kim, Synthesis of optically active 2-hydroxy monoesters via-kinetic resolution and asymmetric cyclization catalyzed by heterometallic chiral (salen) Co complex, Tetrahedron Lett., 47, 3453-3457 (2006).   DOI
12 S. S. Thakur, W. Li, C.-K. Shin, and G.-J. Kim, Asymmetric ring opening of terminal epoxides via kinetic resolution catalyzed by new bimetallic chiral (salen) Co complexes, Chirality, 18, 37-43 (2006).   DOI
13 S. S. Thakur, S.-W. Chen, W. Li, C.-K. Shin, S. J. Kim, Y. M. Koo, and G.-J. Kim, A new dinuclear chiral salen complexes for asymmetric ring opening and closing reactions: Synthesis of valuable chiral intermediates, J. Orgnomet. Chem., 691, 1862-1872 (2006).   DOI
14 S.-W. Chen, S. S. Thakur, W. Li, C.-K. Shin, R. B. Kawthekar, and G.-J. Kim, Efficient catalytic synthesis of optically pure 1,2-azido alcohols through enantioselective epoxide ring opening with $HN_3$, J. Mol. Catal A, 259, 116-120 (2006).   DOI
15 L. P. C. Nielson, C. P. Stevenson, D. G. Backmond, and E. N. Jacobsen, Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides, J. Am. Chem. Soc., 126, 1360-1362 (2004).   DOI
16 S. D. Bose and A. V. Narsaiah, An efficient asymmetric synthesis of (S)-atenolol: using hydrolytic kinetic resolution, Bioorg. Med. Chem., 13, 627-630 (2005).   DOI
17 J. M. Klunder, T. Onami, and K. B. Sharpless, Arenesulfonate derivatives of homochiral glycidol: Versatile chiral building blocks for organic synthesis, J. Org. Chem., 54, 1295-1304 (1989).   DOI
18 K. Ogawa, S. Ohta, and M. Okamoto, Reaction of terminal oxiranes with arenesulfonic acid, Synthesis, 3, 281-284 (1987).