Devendran Saravanan, Yadav Ganapati D
Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Mumbai-400019, India.
Chirality. 2014 Jun;26(6):286-92. doi: 10.1002/chir.22317. Epub 2014 Apr 15.
S-1-(2-Furyl) ethanol serves as an important chiral building block for the preparation of various natural products, fine chemicals, and is widely used in the chemical and pharmaceutical industries. In this work, lipase-catalyzed kinetic resolution of (R/S)-1-(2-furyl) ethanol using different acyl donors was investigated. Vinyl esters are good acyl donors vis-à-vis alkyl esters for kinetic resolution. Among them, vinyl acetate was found to be the best acyl donor. Different immobilized lipases such as Rhizomucor miehei lipase, Thermomyces lanuginosus lipase, and Candida antarctica lipase B were evaluated for this reaction, among which C. antarctica lipase B, immobilized on acrylic resin (Novozym 435), was found to be the best catalyst in n-heptane as solvent. The effect of various parameters was studied in a systematic manner. Maximum conversion of 47% and enantiomeric excess of the substrate (ees ) of 89% were obtained in 2 h using 5 mg of enzyme loading with an equimolar ratio of alcohol to vinyl acetate at 60 °C at a speed of 300 rpm in a batch reactor. From the analysis of progress curve and initial rate data, it was concluded that the reaction followed the ordered bi-bi mechanism with dead-end ester inhibition. Kinetic parameters were obtained by using nonlinear regression. This process is more economical, green, and easily scalable than the chemical processes.
S-1-(2-呋喃基)乙醇是制备各种天然产物、精细化学品的重要手性结构单元，在化学和制药工业中广泛应用。在本工作中，研究了使用不同酰基供体，通过脂肪酶催化对映体选择性拆分(R/S)-1-(2-呋喃基)乙醇。相对于烷基酯，乙烯基酯是对映体选择性拆分中良好的酰基供体。其中，乙酸乙烯酯被发现是最佳的酰基供体。评估了不同的固定化脂肪酶，如米黑根毛霉脂肪酶、嗜热栖热菌脂肪酶和南极假丝酵母脂肪酶B用于该反应，其中固定在丙烯酸树脂上的南极假丝酵母脂肪酶B（诺维信435）在正庚烷作为溶剂时被发现是最佳催化剂。系统地研究了各种参数的影响。在间歇反应器中，于60℃、300 rpm转速下，使用5 mg酶负载量，醇与乙酸乙烯酯等摩尔比，在2 h内获得了47%的最大转化率和89%的底物对映体过量值（ees）。通过对反应进程曲线和初始速率数据的分析，得出该反应遵循有序双底物双产物机制且存在终产物酯抑制作用的结论。通过非线性回归获得了动力学参数。该过程比化学过程更经济、绿色且易于放大。
