CaL-B a highly selective biocatalyst for the kinetic resolution of furylbenzthiazole-2-yl-ethanols and acetates

Abstract A highly stereoselective enzymatic kinetic resolution of novel various substituted racemic furylbenzthiazole-2-yl-ethanols and their acetates has been developed. Both processes, the enzymatic acylation of the racemic alcohols and the enzymatic methanolysis of racemic acetates yielded highly enantiomerically enriched (ee >98%) resolution product, when CaL-B was used as a biocatalyst in acetonitrile. The absolute configuration of the obtained ( R )-(+)-1-(5-(4-chlorobenzo[d]thiazol-2-yl)furan-2-yl)ethanol was determined by a detailed 1 H NMR study of rac - and (+)-1-(5-(4-chlorobenzo[ d ]thiazol-2-yl)furan-2-yl)ethanol Mosher derivatives.

[1]  J. Dutcher,et al.  Pentacyclic triterpene synthesis. 5. Synthesis of optically pure ring AB precursors , 1976 .

[2]  Lipase-mediated chiral resolution of racemates in organic solvents , 2004 .

[3]  H. Nishino,et al.  Acid-catalyzed convenient transformation of 1-aryl-2-pentene-1,4-diones into polyfunctionalized furans , 2000 .

[4]  G. Karminski-Zamola,,et al.  Absorption and Fluorescence Properties of Some Substituted 2‐Furylbenzothiazoles and Their Vinylogues in Various Solvents , 2003 .

[5]  Wolfgang Lindner,et al.  Chirality in drug research , 2006 .

[6]  R. Kazlauskas,et al.  Determination of absolute configuration of secondary alcohols using lipase-catalyzed kinetic resolutions. , 2008, Chirality.

[7]  Paula Moldovan,et al.  Lipase-catalyzed kinetic resolution of racemic 1-heteroarylethanols-experimental and QM/MM study , 2008 .

[8]  T. Kusumi,et al.  High-field FT NMR application of Mosher's method. The absolute configurations of marine terpenoids , 1991 .

[9]  A. Chadha,et al.  Asymmetric reduction of alkyl 2-oxo-4-arylbutanoates and -but-3-enoates by Candida parapsilosis ATCC 7330: assignment of the absolute configuration of ethyl 2-hydroxy-4-(p-methylphenyl)but-3-enoate by 1H NMR , 2004 .

[10]  Lee Chee Keong,et al.  Kinetic resolutions with novel, highly enantioselective fungal lipases produced by solid state fermentation , 2006 .

[11]  B. A. Keay,et al.  Synthesis of multi-substituted furan rings: the role of silicon , 1999 .

[12]  B. Lipshutz Five-membered heteroaromatic rings as intermediates in organic synthesis , 1986 .

[13]  B. Potter,et al.  Discovery of novel inhibitors of human 11β-hydroxysteroid dehydrogenase type 1 , 2009, Molecular and Cellular Endocrinology.

[14]  H. M. Doesburg,et al.  The structure of the (2R)‐3,3,3‐trifluoro‐2‐methoxy‐2‐phenylpropionic acid ester of trans‐4‐tert‐butylcyclohexanol , 1982 .

[15]  C. Wawrzeńczyk,et al.  Kinetic resolution of racemic secondary aliphatic allylic alcohols in lipase-catalyzed transesterification , 2007 .

[16]  Liron Levy,et al.  Trends in the development of chiral drugs. , 2004, Drug discovery today.

[17]  A. Kamal,et al.  Approaches based on enzyme mediated kinetic to dynamic kinetic resolutions: A versatile route for chiral intermediates , 2008 .

[18]  H. Mosher,et al.  Correlation of configuration and fluorine-19 chemical shifts of .alpha.-methoxy-.alpha.-trifluoromethylphenyl acetate derivatives , 1973 .

[19]  O. Alagoz,et al.  Free Radical Cyclization of 1,3‐Dicarbonyl Compounds Mediated by Manganese(III) Acetate with Alkynes and Synthesis of Tetrahydrobenzofurans, Naphthalene, and Trifluoroacetyl Substituted Aromatic Compounds , 2006 .

[20]  Csaba Paizs,et al.  Synthesis of enantiomerically enriched (R)- and (S)-benzofuranyl- and benzo[b]thiophenyl-1,2-ethanediols via enantiopure cyanohydrins as intermediates , 2010 .

[21]  J. Goodman,et al.  A route to enantiomerically pure 5-(2′-hydroxyethyl)cyclopent-2-en-1-ol and its absolute configuration by Mosher esters , 2009 .

[22]  Csaba Paizs,et al.  Candida antarctica lipase A in the dynamic resolution of novel furylbenzotiazol-based cyanohydrin acetates , 2003 .

[23]  M. Zając,et al.  Donor–π-acceptor benzothiazole-derived dyes with an extended heteroaryl-containing conjugated system: synthesis, DFT study and antimicrobial activity , 2008 .

[24]  W. Butler,et al.  Nonempirical confirmations of the absolute configuration of (+)-.alpha.-methoxy-.alpha.-(trifluoromethyl)phenylacetic acid , 1989 .

[25]  M. Kralj,et al.  Novel amidino substituted 2-phenylbenzothiazoles: synthesis, antitumor evaluation in vitro and acute toxicity testing in vivo. , 2010, Bioorganic & medicinal chemistry.

[26]  Aviva Rappaport,et al.  A rule to predict which enantiomer of a secondary alcohol reacts faster in reactions catalyzed by cholesterol esterase, lipase from Pseudomonas cepacia, and lipase from Candida rugosa , 1991 .

[27]  B. Potter,et al.  Benzothiazole derivatives as novel inhibitors of human 11β-hydroxysteroid dehydrogenase type 1 , 2006, Molecular and Cellular Endocrinology.

[28]  H. Mosher,et al.  Nuclear magnetic resonance enantiomer regents. Configurational correlations via nuclear magnetic resonance chemical shifts of diastereomeric mandelate, O-methylmandelate, and .alpha.-methoxy-.alpha.-trifluoromethylphenylacetate (MTPA) esters , 1973 .