Improved racemate resolution of pentan-2-ol and trans -( Z )-cyclooct-5-ene-1,2-diol by lipase catalysis

Abstract

Lipases are important catalysts in chiral synthesis due to their wide substrate recognition combined with a high stereoselectivity. We demonstrate here that the state, free or immobilized, of Candida antarctica lipase B (CaLB) affects enantioselectivity and also alters the temperature dependancy of the enzyme. This indicates that CaLB undergoes various conformations induced by its interaction with the different immobilization supports studied. Molecular imprinting experiments, using immobilized enzyme co-dried with mimic substrate molecules, enhanced the enantiomeric ratio two-fold or three-fold, depending on the immobilization support. The structure of the acyl donor has a pronounced effect on CaLB catalyzed resolution, due to the proximity of the acyl and alcohol moieties during catalysis. When the acylation of pentan-2-ol was examined, we found that the 3C methyl propanoate donor afforded the highest resolution. Trans-(Z)-cyclooct-5-en-1,2-diol was used as a model racemic substrate to study the ability of lipase to catalyze the resolution of difunctionalized compounds. There was a clear enhancement in the enantiomer selectivity of the biotransformation of the diol when vinyl butanoate is used as the acyl donor. The conversion and enantiomeric excess of (1R,2R)-monoacetates were enhanced, using immobilized CaLB, when the chain length of the donors increased from C2 to C4.

Efficient production of wild-type lipase B from Candida antarctica in the cytoplasm of Escherichia coli

“…It remains stable from pH 3.5 -9.5 (optimal catalysis at pH 7) and has been observed to function at 150°C [4], in polar organic solvents [5], within ionic liquids and supercritical carbon dioxide [4]. The enzyme is an efficient biocatalyst and can be utilized in a broad range of processes, from biodiesel production (reviewed in [6][7][8][9][10][11][12]), glycerol carbonate [13], diacylglycerol [14][15], benzyl acetate [16], olvanil [17] and drug synthesis, [18] racemate resolutions [19][20][21][22][23], lignin valorization [24] and aminolysis [25].…”

Lipase Immobilized Metal‐Organic Frameworks as Remarkably Biocatalyst for Ester Hydrolysis: A One Step Approach for Lipase Immobilization

“…Extensive specificity and wide range of catalytic reaction make Lipase versatile. Hence in this work, Lipase is chosen as an archetypical enzyme . In the past decade, many attempts were reported for the immobilization of lipase using various types of supports .…”

Yeşil Çözücü Ortamında Enzimatik Kinetik Rezolüsyon Yöntemi ile Enantiyomerik Saflıkta 1-Feniletanol Üretimi

“…GİRİŞ (INTRODUCTION) Geçtiğimiz yıllarda, ilaç endüstrisinde kiralitenin etkilerinin bilinmemesinden ötürü yaşanan olumsuzluklar günümüzde kiralitenin önemi ve biyolojik aktiviteyle güçlü ilişkisine yönelik farkındalık oluşturmuş ve böylelikle enantiyomerik saflıkta bileşiklerin daha düşük maliyetle geliştirilmesine yönelik büyük bir ihtiyaç yaratmıştır [1][2][3][4]. Bu zamana kadar anestezik, antibiyotik, anti-kanser, kardiyovasküler vb.…”