Abstract
Isooctane was the best reaction medium for the enantioselective esterification of (R,S)-2-methylalkanoic acid with n-butanol using Carica papaya lipase as catalyst. Increasing linear alkyl-chain length of racemic 2-methylalkanoic acids from ethyl to hexyl increased the enantioselectivity (E) from 2.1 to 98.2 for the esterification of racemic 2-methylalkanoic acids with n-butanol at 35°C. Decreasing reaction temperature from 40 to 20°C increased the enantioselectivity (E) from 14 to 33 for the esterification of racemic 2-methylhexanoic acids with n-butanol. We obtained a maximum enantioselectivity, of E = 24.3, for the enantioselective esterification of racemic 2-methylhexanoic acids with n-butanol in isooctane at water activity 0.33, and at 35°C.
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References
Ahmed SN, Kazlauskas RJ, Morinville AH, Grochulski P, Schrag JD, Cygler M (1994) Enantioselectivity of Candida rugosa lipase towards carboxylic acids: a predictive rule from substrate mapping and X-ray crystallography. Biocatalysis 9:209–225
Berglund P, Holmquist M, Hedenström E, Hult K, Högberg HE (1993) 2-Methylalkanoic acids resolved by esterification catalysed by lipase from Candida rugosa: alcohol chain length and enantioselectivity. Tetrahedron Asymmetr 4:1869–1878
Berglund P, Holmquist M, Hult K, Högberg HE (1995) Alcohols as enantioselective inhibitors in a lipase catalysed esterification of a chiral acyl donor. Biotechnol Lett 17:55–60
Caro Y, Pina M, Turon F, Guilbert S, Mougeout E, Fetsch DV, Attwool P, Graille J (2002) Plant lipases: biocatalyst aqueous environment in relation to optimal catalytic activity in lipase-catalyzed synthesis reactions. Biotechnol Bioeng 77:693–703
Chen CC, Tsai SW (2005) Carica papaya lipase: a novel biocatalyst for the enantioselective hydrolysis of (R,S)-naproxen 2,2,2-trifluoroethyl ester. Enzyme Microb Technol 36:127–132
Cheng YC, Tsai SW (2004) Enantioselective esterification of (R,S)-2-(4-chlorophenoxy)-propionic acid via Carica papaya lipase in organic solvents. Tetrahedron Asymmetr 15:2917–2920
Domínguez de María P, Sinisterra JV, Tsai SW, Alcántara AR (2006) Carica papaya lipase: an emerging and versatile biocatalyst. Biotechnol Adv 24:493–499
Engel KH (1991) Lipase-catalyzed enantioselective esterification of 2-methylalkanoic acids. Tetrahedron Asymmetr 2:165–168
Fitzpatrick PA, Klibanov AM (1991) How can the solvent affect enzyme enantioselectivity? J Am Chem Soc 113:3166–3171
Heinsman NWJT, Franssen MCR, Van Der Padt A, Boom RM, Van’t Riet K, De Groot AE (2002) Lipase-mediated resolution of branched chain fatty acids. Biocatal Biotransform 20:297–309
Högberg HE, Edlund H, Berglund P, Hedenström E (1993) Water activity influences enantioselectivity in a lipase-catalysed resolution by esterification in an organic solvent. Tetrahedron Asymmetr 4:2123–2126
Holmberg E, Hoimquist M, Hedenström E, Berglund P, Norin T, Högberg HE, Hult K (1991) Reaction conditions for the resolution of 2-methylalkanoic acids in esterification and hydrolysis with lipase from Candida cylindracea. Appl Microbiol Biotechnol 35:572–578
Krishna SH, Karanth NG (2002) Lipases and lipase-catalyzed esterification reactions in nonaqueous media. Catal Rev 44:499–591
Kwon DY, Hong YJ, Yoon SH (2000) Enantiomeric synthesis of (S)-2-methylbutanoic acid methyl ester, apple flavor, using lipases in organic solvent. J Agric Food Chem 48:524–530
Laane C, Boeren S, Vos K, Veeger C (1987) Rules for optimization of biocatalysis in organic solvents. Biotechnol Bioeng 30:81–87
Maciel MI, Hansen TJ, Aldinger SB, Labows JN (1986) Flavor chemistry of cashew apple juice. J Agric Food Chem 34:923–927
Macleod AJ, Pieris NM (1981) Volatile flavor components of beli fruit (Aegle marmelos) and a processed product. J Agric Food Chem 29:49–53
Miyazawa T, Onishi K, Murashima T, Yamada T, Tsai SW (2005) Resolution of non-protein amino acids via Carica papaya lipase-catalyzed enantioselective transesterification. Tetrahedron Asymmetr 16:2569–2573
Nakamura K, Kinoshita M, Ohno A (1995) Structure of solvent affects enantioselectivity of lipase-catalyzed transesterification. Tetrahedron 51:8799–8808
Ng IS, Tsai SW (2005) Partially purified Carica papaya lipase: a versatile biocatalyst for the hydrolytic resolution of (R,S)-2-arylpropionic thioesters in water-saturated organic solvents. Biotechnol Bioeng 91:106–113
Nguyen BV, Hedenström E (1999) Candida rugosa lipase as an enantioselective catalyst in the esterification of methyl branched carboxylic acids: resolution of rac-3,7-dimethyl-6-octenoic acid (citronellic acid). Tetrahedron Asymmetr 10:1821–1826
Parida S, Dordick JS (1991) Substrate structure and solvent hydrophobicity control lipase catalysis in organic media. J Am Chem Soc 113:2253–2259
Pleiss J, Fischer M, Schmid RD (1998) Anatomy of lipase binding sites: the scissile fatty acid binding site. Chem Phys Lipids 93:67–80
Sabbani S, Hedenström E (2009) Control of water activity in lipase catalysed esterification of chiral alkanoic acids. J Mol Catal B: Enzym 58:6–9
Sabbani S, Hedenström E, Nordin O (2006) The enantioselectivity of Candida rugosa lipase is influenced by the particle size of the immobilising support material Accurel. J Mol Catal B: Enzym 42:1–9
Um PJ, Drueckhammer DG (1998) Dynamic enzymatic resolution of thioesters. J Am Chem Soc 120:5605–5610
Villeneuve P (2003) Plant lipases and their applications in oils and fats modification. Eur J Lipid Sci Technol 105:308–317
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The authors would like to thank the National Science Council of the Republic of China, Taiwan, for financially supporting this research under Contract No. NSC- 96-2221-E-218 -029.
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Chang, CS., Ho, SC. Enantioselective esterification of (R,S)-2-methylalkanoic acid with Carica papaya lipase in organic solvents. Biotechnol Lett 33, 2247–2253 (2011). https://doi.org/10.1007/s10529-011-0692-7
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DOI: https://doi.org/10.1007/s10529-011-0692-7