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Synlett 2005(11): 1746-1748
DOI: 10.1055/s-2005-871548
DOI: 10.1055/s-2005-871548
LETTER
© Georg Thieme Verlag Stuttgart · New York
Improved Process for the Enantioselective Hydrolysis of Prochiral Diethyl Malonates Catalyzed by Pig Liver Esterase
Further Information
Received
22 February 2005
Publication Date:
14 June 2005 (online)
Publication History
Publication Date:
14 June 2005 (online)
Abstract
An improved process for the enantioselective hydrolysis of prochiral 2-aryl-2-alkyl-disubstituted diethyl malonates catalyzed by pig liver esterase (PLE) was developed. With diethyl 2-phenyl-2-methylmalonate as a model substrate, the highest enantioselectivities (96% ee; R-isomer) were achieved when carrying out the process in the presence of a suitable mixture of cosolvents (buffer-i-PrOH-t-BuOH, 8:1:1). The process also works efficiently at higher substrate concentrations. The reaction was carried out on a multi-gram preparative scale, leading to a conversion of >95%, an enantioselectivity of 96% ee, and a yield of 83% at a substrate concentration of 200 mM.
Key words
asymmetric synthesis - enzymes - hydrolyses - malonates - solvent effects
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Patel R.Banerjee A.Chu L.Brozozowski D.Nanduri V.Szarka LJ. J. Am. Oil Chem. Soc. 1998, 75: 1473 - 2
Fadel A.Arzel P. Tetrahedron: Asymmetry 1995, 6: 893 - 3
Fadel A.Garcia-Argote S. Tetrahedron: Asymmetry 1996, 7: 1159 - 4
Fadel A.Vandromme L. Tetrahedron: Asymmetry 1999, 10: 1153 - 5
Drauz K.Waldmann H. Enzyme Catalysis in Organic Synthesis 2nd Ed., Vol.: Wiley-VCH; Weinheim: 2002. Chap. 11. - 6
Klotz-Berendes B.Kleemiss W.Jegelka U.Schäfer HJ.Kotila S. Tetrahedron: Asymmetry 1997, 8: 1821 - 7
Musidlowska A.Lange S.Bornscheuer UT. Angew. Chem. Int. Ed. 2001, 40: 2851 ; interestingly, remarkable differences in enantioselectivities between commercially available crude PLE and the recombinant PLE-isoenzyme are reported therein - 8
Toone E.Jones B. Tetrahedron: Asymmetry 1991, 2: 1041 - 9
Schneider M.Engel N.Boensmann H. Angew. Chem., Int. Ed. Engl. 1984, 23: 64 ; Angew. Chem. 1984, 96, 54 - 10
Björkling F.Boutelje J.Gatenbeck S.Hult K.Norin T. Tetrahedron Lett. 1985, 26: 4957 - 11
Guanti G.Banfi L.Narisano E.Riva R.Thea S. Tetrahedron Lett. 1986, 27: 4639 - 12
Guanti G.Banfi L.Narisano E. Tetrahedron Lett. 1989, 30: 2697 - 13
Lam LKP.Raymond AHF.Jones JB. J. Org. Chem. 1986, 51: 2047 - 14
Chartrain M.Maligres P.Cohen D.Upadhyay V.Pecore V.Askin D.Greashan R. J. Biosci. Bioeng. 1999, 87: 386 - 15
Arzel P.Freida V.Weber P.Fadel A. Tetrahedron: Asymmetry 1999, 10: 3877