Dynamic kinetic resolution of tert-alcohols via combination of a lipase/Brønsted acid in a biphasic reaction medium

Kin, Takusho; Horino, Satoshi; Moon, Jihoon et al.

Green Chemistry, 2025

Number of Access:11（2025-08-17 20:36 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/102428

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Title
Dynamic kinetic resolution of tert-alcohols via combination of a lipase/Brønsted acid in a biphasic reaction medium
Creator
CreatorName
Kin, Takusho
CreatorName
Horino, Satoshi
CreatorName
Moon, Jihoon
CreatorName
Tsuda, Momoka
CreatorName
Gröger, Harald
NRID
1000060192457 1000060192457
ORCID
0000-0001-9149-8745 0000-0001-9149-8745
researchmap permalink
shuji_akai shuji_akai
Scopus Author ID
7006001526 7006001526
CreatorName
Akai, Shuji
NRID
1000030880447 1000030880447
ORCID
0000-0002-2251-4665 0000-0002-2251-4665
researchmap permalink
kyohei_kanomata kyohei_kanomata
Scopus Author ID
39861733600 39861733600
CreatorName
Kanomata, Kyohei
Description
Reproduced from Green Chem., 2025 with permission from the Royal Society of Chemistry.
Abstract
Chemoenzymatic dynamic kinetic resolution (DKR) provides a promising green approach for synthesizing optically active alcohols and their derivatives, which serve as widely used key intermediates in the fine chemical industry. While lipase-catalysed DKR of secondary alcohols has been extensively studied, the DKR of tertiary alcohols remains a significant challenge, even in advanced organic synthesis. This is mainly because tert-alcohols are poorly reactive to esterification owing to steric hindrance and are prone to dehydrative side reactions. In this study, the combined use of a lipase and the strong Brønsted acid H₂SO₄ enabled the efficient DKR of racemic tert-alcohols to produce the corresponding esters with high enantiomeric excess (95–99% ee) in 56–91% isolated yields. In this DKR system, lipase-catalysed kinetic resolution in the oil phase and H₂SO₄-catalysed racemization of the unreacted enantiomer of the alcohol in the aqueous phase proceeded concurrently in one reactor. This simultaneous use of the inherently incompatible combination of a lipase and a strong Brønsted acid was realized by integrating phase separation via a hydrophobic polydimethylsiloxane membrane and a recycling flow reaction system. In addition, side reactions were completely suppressed by conducting the racemization reaction in the aqueous phase, enabling the application of this DKR methodology to a range of tert-alcohols, thus demonstrating, for the first time, a generally applicable DKR system for tert-alcohols.
Publisher
Royal Society of Chemistry (RSC)
Source Title
Green Chemistry
Date of Issued
2025-07-10
Language
English
Handle URL
https://hdl.handle.net/11094/102428
PISSN
14639262
eISSN
14639270
Relation.isVersionOf
DOI (Publisher Version)
https://doi.org/10.1039/D4GC06535B
Access Rights
embargoed access
CopyRight
Reproduced from Green Chem., 2025 with permission from the Royal Society of Chemistry.
The full-text file will be made open to the public on 10 July 2026 in accordance with the publisher's policy.
oaire:version
Accepted Manuscript
Category
学術雑誌論文 Journal Article