Kawanishi Shinji, Oki Shinya, Kundu Dhiman, Akai Shuji
Graduate School of Pharmaceutical Sciences , Osaka University , Yamadaoka 1-6 , Suita , Osaka 565-0871 , Japan.
Org Lett. 2019 May 3;21(9):2978-2982. doi: 10.1021/acs.orglett.9b00334. Epub 2019 Mar 15.
Quantitative conversion of racemic propargyl alcohols into optically active propargyl esters with up to 99% ee has been achieved by lipase/oxovanadium co-catalyzed dynamic kinetic resolution, which combines the lipase-catalyzed enantioselective esterification of the racemic substrates and the in situ racemization of the remaining enantiomers. The success is owed to our discovery of a magic solvent, (trifluoromethyl)benzene, that accelerated the racemization while sufficiently suppressing the common oxovanadium-catalyzed rearrangement of propargyl alcohols to irreversibly produce enals.
通过脂肪酶/氧钒共催化的动态动力学拆分，已实现将外消旋炔丙醇定量转化为对映体过量高达99%的光学活性炔丙酯，该过程结合了脂肪酶催化的外消旋底物对映选择性酯化和剩余对映体的原位外消旋化。这一成功归功于我们发现了一种神奇的溶剂——（三氟甲基）苯，它加速了外消旋化，同时充分抑制了常见的氧钒催化的炔丙醇重排，从而不可逆地生成烯醛。
