Lipase/Oxovanadium Co-Catalyzed Dynamic Kinetic Resolution of Propargyl Alcohols: Competition between Racemization and Rearrangement

Shinji Kawanishi; Shinya Oki; Dhiman Kundu; Shuji Akai

doi:10.1021/acs.orglett.9b00334

Lipase/Oxovanadium Co-Catalyzed Dynamic Kinetic Resolution of Propargyl Alcohols: Competition between Racemization and Rearrangement

Shinji Kawanishi, Shinya Oki, Dhiman Kundu, Shuji Akai

Bioregulation

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19 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	2978-2982
Number of pages	5
Journal	Organic letters
Volume	21
Issue number	9
DOIs	https://doi.org/10.1021/acs.orglett.9b00334
Publication status	Published - May 3 2019

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/acs.orglett.9b00334

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title = "Lipase/Oxovanadium Co-Catalyzed Dynamic Kinetic Resolution of Propargyl Alcohols: Competition between Racemization and Rearrangement",

abstract = "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.",

author = "Shinji Kawanishi and Shinya Oki and Dhiman Kundu and Shuji Akai",

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doi = "10.1021/acs.orglett.9b00334",

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T2 - Competition between Racemization and Rearrangement

AU - Kawanishi, Shinji

AU - Oki, Shinya

AU - Kundu, Dhiman

AU - Akai, Shuji

N1 - Funding Information: This work was financially supported by the JSPS KAKENHI [16H01151/18HO4411 (Middle Molecular Strategy) and 18H02556] and AMED (Grant 18am0101084j). Publisher Copyright: © 2019 American Chemical Society.

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N2 - 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.

AB - 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.

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Lipase/Oxovanadium Co-Catalyzed Dynamic Kinetic Resolution of Propargyl Alcohols: Competition between Racemization and Rearrangement

Abstract

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