Molecular Sciences Institute School of Chemistry, University of the Witwatersrand Private Bag X3, PO WITS, Johannesburg, 2050, South Africa.
Department of Biotechnology Section BOC, Delft University of Technology, van der Maasweg 9, 2629 HZ, Delft, The Netherlands.
Chembiochem. 2022 Nov 4;23(21):e202200435. doi: 10.1002/cbic.202200435. Epub 2022 Sep 29.
Acylated Morita-Baylis-Hillman (MBH) adducts were synthesised and subjected to enzymatic kinetic resolution (EKR) by hydrolysis employing various lipase enzymes: from P. fluorescens, P. cepacia (PCL), C. antarctica A (CAL-A), C. antarctica B (CAL-B) and Novozyme 435. In a number of instances enantiopure Morita-Baylis-Hillman acetates or butyrates and their corresponding hydrolysed MBH adducts were obtained with ee values of >90 %, at ca. 50 % conversion, corresponding to enantiomeric ratio (E) values of >200. Enantioselective transesterification reactions on MBH adducts was achieved using acyl anhydrides in THF or the greener organic solvent 2-MeTHF in the presence of CAL-A. This is the first report of successful lipase-catalysed EKR of aromatic MBH adducts by transesterification in organic medium.
酰化的 Morita-Baylis-Hillman (MBH) 加合物被合成，并通过水解用各种脂肪酶酶进行酶促动力学拆分 (EKR)：来自荧光假单胞菌、假单胞菌 Cepacia (PCL)、南极假丝酵母 A (CAL-A)、南极假丝酵母 B (CAL-B) 和 Novozyme 435。在许多情况下，获得了对映体纯的 Morita-Baylis-Hillman 乙酸酯或丁酸酯及其相应的水解 MBH 加合物，ee 值>90%，转化率约为 50%，对应对映体过量值 (E) 值>200。使用酰基酐在 THF 或更环保的有机溶剂 2-MeTHF 中，在 CAL-A 的存在下，对 MBH 加合物进行对映选择性酯交换反应。这是首次报道在有机介质中通过酯交换成功地用脂肪酶催化芳香族 MBH 加合物的 EKR。
