Enantiodivergent Chemoenzymatic Dynamic Kinetic Resolution: Conversion of Racemic Propargyl Alcohols into Both Enantiomers
Enantiodivergent Chemoenzymatic Dynamic Kinetic Resolution: Conversion of Racemic Propargyl Alcohols into Both Enantiomers
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对映体趋异化学酶动态动力学拆分：外消旋炔丙醇转化为两种对映体
DOI：
10.1002/chem.202202437
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Akai Shuji
中科院分区：
文献类型：
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作者：
Horino Satoshi;Nishio Tomoya;Kawanishi Shinji;Oki Shinya;Nishihara Koichi;Ikawa Takashi;Kanomata Kyohei;Wagner Karla;Gr?ger Harald;Akai Shuji
天然脂肪酶通常基于甲醇部分附近取代基的大小差异识别醇的对映体，并选择性地与仲醇的对映体反应。因此，外消旋仲醇的脂肪酶催化动态动力学拆分（DKR）仅产生对映体。本文报道了一种通过DKR仲3-（三烷基甲硅烷基）炔丙醇来获得S对映体的方法，该方法通过使用众所周知的R-选择性假单胞菌荧光脂酶与外消旋催化剂VMPS 4组合来进行，其中甲硅烷基逆转了甲醇部分附近取代基的大小关系。我们已经在乙炔基末端碳上没有取代基的相应炔丙醇的R-选择性DKR，并且容易除去的甲硅烷基的存在使我们能够以高化学产率和高对映体过量产生炔丙醇的两种对映体。此外，发现在硅藻土上固定化脂肪酶对于实现DKR的高效率是重要的。
Natural lipases typically recognize enantiomers of alcohols based on the size differences of substituents near the carbinol moiety and selectively react with theRenantiomers of secondary alcohols. Therefore, lipase‐catalyzed dynamic kinetic resolution (DKR) of racemic secondary alcohols produces onlyRenantiomers. We report herein a method for obtainingSenantiomers by DKR of secondary 3‐(trialkylsilyl)propargyl alcohols by using a well‐knownR‐selectivePseudomonas fluorescenslipase in combination with a racemization catalyst VMPS4, in which the silyl group reverses the size relationship of substituents near the carbinol moiety. We have already reportedR‐selective DKR of the corresponding propargyl alcohols without substituents on the ethynyl terminal carbon, and the presence of an easily removable silyl group has enabled us to produce both enantiomers of propargyl alcohols in high chemical yields and with high enantiomeric excess. In addition, immobilization of the lipase on Celite was found to be important for achieving a high efficiency of the DKR.