Kołodziejska Renata, Studzińska Renata, Pawluk Hanna
Department of Biochemistry, Faculty of Medicine, Nicolaus Copernicus University in Toruń, Collegium Medicum in Bydgoszcz, Bydgoszcz, Poland.
Department of Organic Chemistry, Faculty of Pharmacy, Nicolaus Copernicus University in Toruń, Collegium Medicum in Bydgoszcz, Bydgoszcz, Poland.
Chirality. 2018 Feb;30(2):206-214. doi: 10.1002/chir.22787. Epub 2017 Nov 15.
The application of ionic liquids as solvents for transesterification of prochiral pirymidine acyclonucleoside using lipase (EC 3.1.1.3) Amano PS from Burkholderia cepacia (BCL) is reported. The effect of using medium reaction, acyl group donor, and temperature on the activity and enantioselectivity of BCL was studied. From the investigated ionic solvents, the hydrophobic ionic liquid [BMIM]PF ] was the preferred medium for enzymatic reactions. However, the best result was obtained in the mixture [BMIM][PF ]:TBME (1:1 v/v) at 50°C. Enzyme activity and selectivity in [BMIM][PF ]:TBME (1:1 v/v) was slightly higher in than in conventional organic solvents (for example, TBME), and in this condition, good activity and enantioselectivity were associated with unique properties of ionic liquid such as hydrophobicity and high polarity. Independently of solvents, monester of (R)-configuration was obtained in excess. Under optimal conditions, desymmetrization of the prochiral compound using different acyl donors was performed. If vinyl butyrate was used as the acylating agent, BCL completely selectively acylated enantiotopic hydroxyl groups.
报道了离子液体作为溶剂，用于洋葱伯克霍尔德菌（BCL）来源的脂肪酶（EC 3.1.1.3）Amano PS催化前手性嘧啶阿糖核苷的酯交换反应。研究了反应介质、酰基供体和温度对BCL活性和对映选择性的影响。在所研究的离子溶剂中，疏水性离子液体[BMIM]PF]是酶促反应的首选介质。然而，在50℃下，[BMIM][PF]：TBME（1:1 v/v）的混合物中得到了最佳结果。[BMIM][PF]：TBME（1:1 v/v）中的酶活性和选择性略高于传统有机溶剂（如TBME），在此条件下，良好的活性和对映选择性与离子液体的独特性质如疏水性和高极性有关。与溶剂无关，过量获得了（R）-构型的单酯。在最佳条件下，使用不同的酰基供体对手性前体化合物进行了去对称化反应。如果使用丁酸乙烯酯作为酰化剂，BCL完全选择性地酰化对映异位羟基。
