Liu Yan, Wang Yali, Jiang Yucheng, Hu Mancheng, Li Shuni, Zhai Quanguo
School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710062, P.R. China.
Key Laboratory of Macromolecular Science of Shaanxi Province, Shaanxi Normal University, Xi'an, 710062, P.R. China.
Biotechnol Prog. 2015 May-Jun;31(3):724-9. doi: 10.1002/btpr.2076. Epub 2015 Apr 14.
The optically active C3 synthetic blocks are remarkably versatile intermediates for the synthesis of numerous pharmaceuticals and agrochemicals. This work provides a simple and efficient enzymatic synthetic route for the environment-friendly synthesis of C3 chiral building blocks. Chloroperoxidase (CPO)-catalyzed enantioselective halo-hydroxylation and epoxidation of chloropropene and allyl alcohol was employed to prepare C3 chiral building blocks in this work, including (R)-2,3-dichloro-1-propanol (DCP*), (R)-2,3-epoxy-1-propanol (GLD*), and (R)-3-chloro-1-2-propanediol (CPD*). The ee values of the formed C3 chiral building blocks DCP*, CPD*, and glycidol were 98.1, 97.5, and 96.7%, respectively. Moreover, the use of small amount of imidazolium ionic liquid enhanced the yield efficiently due to the increase of solubility of hydrophobic organic substrates in aqueous reaction media, as well as the improvement of affinity and selectivity of CPO to substrate.
具有光学活性的C3合成砌块是用于合成众多药物和农用化学品的极为通用的中间体。这项工作为环境友好型合成C3手性结构单元提供了一条简单高效的酶促合成路线。在这项工作中，采用氯过氧化物酶（CPO）催化氯丙烯和烯丙醇的对映选择性卤代羟基化和环氧化反应来制备C3手性结构单元，包括（R）-2,3-二氯-1-丙醇（DCP*）、（R）-2,3-环氧-1-丙醇（GLD*）和（R）-3-氯-1,2-丙二醇（CPD*）。所形成的C3手性结构单元DCP*、CPD*和缩水甘油的对映体过量值（ee值）分别为98.1%、97.5%和96.7%。此外，由于疏水性有机底物在水相反应介质中的溶解度增加，以及CPO对底物的亲和力和选择性提高，使用少量咪唑鎓离子液体有效地提高了产率。
