Enantiodivergent Chemoenzymatic Dynamic Kinetic Resolution: Conversion of Racemic Propargyl Alcohols into Both Enantiomers. Issue 60 (7th October 2022)

• Record Type: Journal Article
• Authors: Horino, Satoshi; Nishio, Tomoya; Kawanishi, Shinji; Oki, Shinya; Nishihara, Koichi; Ikawa, Takashi; Kanomata, Kyohei; Wagner, Karla; Gröger, Harald; Akai, Shuji
• Is Part Of: Chemistry. Volume 28:Issue 60(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-10-07
• Subjects: dynamic kinetic resolution -- immobilization -- lipases -- mesoporous silica -- propargyl alcohol -- racemization; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202202437
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Natural lipases typically recognize enantiomers of alcohols based on the size differences of substituents near the carbinol moiety and selectively react with the R enantiomers of secondary alcohols. Therefore, lipase‐catalyzed dynamic kinetic resolution (DKR) of racemic secondary alcohols produces only R enantiomers. We report herein a method for obtaining S enantiomers by DKR of secondary 3‐(trialkylsilyl)propargyl alcohols by using a well‐known R ‐selective Pseudomonas fluorescens lipase 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 reported R ‐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. Abstract : Choosing the outcome : A silyl group at the alkyne terminal of secondary propargyl alcohols temporarily inverted the enantio‐recognition of natural lipases. Using this phenomenon, the lipase/oxovanadium co‐catalyzed dynamic kinetic resolution (DKR) of racemic alcohols achieved enantiodivergent production of R and S enantiomers in high yield and with high enantiomeric excess.