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Chemoenzymatic Dynamic Kinetic Resolution Protocol with an Immobilized Oxovanadium as a Racemization Catalyst
The Journal of Organic Chemistry ( IF 3.6 ) Pub Date : 2024-05-02 , DOI: 10.1021/acs.joc.3c02703
Jiarui Chen 1 , Lingqin Min 1 , Fanxu Meng 1 , Yiwen Fu 1 , Junhong Liu 1 , Yuanyuan Zhang 1
Affiliation  

An excellent compatible and cost-effective dynamic kinetic resolution (DKR) protocol has been developed by combining a novel immobilized oxovanadium racemization catalyst onto cheap diatomite (V-D) with an immobilized lipase LA resolution catalyst onto a macroporous resin (LA-MR). V-D was prepared via grinding immobilization, which may become a promising alternative for the immobilization of metals, especially precious metals due to its low cost, high efficiency, easy separation, and large reaction interface. The DKR afforded high yield (96.1%), e.e. (98.67%), and Sel (98.28%) under optimal conditions established using response surface methodology as follows: the amount of V-D 10.83 mg, reaction time 51.2 h, and temperature 48.1 °C, respectively, indicating that all the reactions in the DKR were coordinated very well. The DKR protocol was also found to have high stability up to six reuses. V-D exhibited excellent compatibility with LA-MR because the lipase immobilized onto MR did not physically contact with the vanadium species immobilized onto diatomite, thus avoiding inactivation. Considering that lipase, oxovanadium, diatomite, and MR used are relatively inexpensive, and the adsorption or grinding immobilization is simple, the LA-V-MD DKR by coupling LA-MR with V-D is a cost-effective and promising protocol for chiral secondary alcohols.

中文翻译:

使用固定化氧钒作为外消旋化催化剂的化学酶动态动力学拆分方案

通过将新型固定化氧钒外消旋催化剂与廉价硅藻土 (VD) 上的固定化脂肪酶 LA 拆分催化剂 (LA-MR) 结合到大孔树脂 (LA-MR) 上,开发了一种出色的兼容性和成本效益的动态动力学拆分 (DKR) 方案。 VD是通过研磨固定化制备的,由于其成本低、效率高、易于分离和反应界面大,可能成为金属特别是贵金属固定化的有前途的替代方案。在使用响应面法建立的最佳条件下,DKR 提供了高产率 (96.1%)、ee (98.67%) 和 Sel (98.28%),如下:VD 量 10.83 mg、反应时间 51.2 h、温度 48.1 °C ,分别表明 DKR 中的所有反应都协调得很好。 DKR 协议还被发现具有高达六次重复使用的高稳定性。 VD 与 LA-MR 表现出优异的相容性,因为固定在 MR 上的脂肪酶不与固定在硅藻土上的钒物质发生物理接触,从而避免了失活。考虑到所使用的脂肪酶、氧钒、硅藻土和 MR 相对便宜,并且吸附或研磨固定化简单,将 LA-MR 与 VD 偶联的 LA-V-MD DKR 是一种经济高效且有前景的手性仲醇方案。
更新日期:2024-05-02
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