Dynamic Kinetic Resolution of 2‐Hydroxybiaryl Atropisomers via Lipase‐Catalyzed Enantioselective O‐Acylation

Dhiman, Neha; Moustafa, Gamal A. I.; Kasama, Kengo et al.

ChemCatChem, 2024, 243, 2904

Number of Access:723（2025-08-17 20:36 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/98130

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Title
Dynamic Kinetic Resolution of 2‐Hydroxybiaryl Atropisomers via Lipase‐Catalyzed Enantioselective O‐Acylation
Creator
CreatorName
Dhiman, Neha
CreatorName
Moustafa, Gamal A. I.
NRID
1000040963236 1000040963236
CreatorName
Kasama, Kengo
NRID
1000060291910 1000060291910
ORCID
0000-0001-7915-8975 0000-0001-7915-8975
researchmap permalink
H_Aoyama H_Aoyama
Scopus Author ID
37042208200 37042208200
CreatorName
Aoyama, Hiroshi
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
CreatorName
Gröger, Harald
NRID
1000060192457 1000060192457
researchmap permalink
shuji_akai shuji_akai
Scopus Author ID
7006001526 7006001526
ORCID
0000-0001-9149-8745 0000-0001-9149-8745
CreatorName
Akai, Shuji
Subject
Acylation
Asymmetric synthesis
Atropisomerism
Biaryls
Density functional calculations
Dynamic kinetic resolution
Lipases
Description
Dhiman Neha, Moustafa Gamal A. I., Kasama Kengo, et al. Dynamic Kinetic Resolution of 2‐Hydroxybiaryl Atropisomers via Lipase‐Catalyzed Enantioselective O‐Acylation. ChemCatChem 243, 2904 (2024); https://doi.org/10.1002/cctc.202400932.
Abstract
The increasing interest in axially chiral biaryl moieties, which are prevalent in chiral ligands, organocatalysts, and bioactive molecules, has raised the need for developing novel efficient synthetic methods for these types of molecules. In addition to the currently available methods, such as kinetic resolution, desymmetrization and enantio- and diastereo-selective biaryl coupling, we herein report a lipase-catalyzed dynamic kinetic resolution (DKR) of racemic 2-hydroxybiaryls through enantioselective O-acylation. This method features the production of enantiomerically enriched atropisomers (89 %–98 % ee) in 91 %–99 % yields from eleven racemates. Notably, the DKR proceeds without any racemization catalyst since in situ-racemization was achieved by easy rotation about the biaryl axis of the substrates. The enzymatic O-acylation then furnished conformationally stable biaryl-containing esters, in which the increased steric bulkiness of the O-acyl moiety suppresses the rotation, i. e., racemization, under the reaction conditions of 35–50 °C. This experimental study was accompanied by a computational determination of the rotational barrier of substrates and products. The choice of suitable substrates with a significant difference in their rotational barrier compared to that of their products turned out to be the key to an efficient implementation of this method.
Publisher
Wiley
Source Title
ChemCatChem
Volume (Issue)
243
Page
2904
Date of Issued
2024-09-11
Language
English
Handle URL
https://hdl.handle.net/11094/98130
PISSN
18673880
eISSN
18673899
Relation.isIdenticalTo
DOI (Publisher Version)
https://doi.org/10.1002/cctc.202400932
Access Rights
open access
CopyRight
This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
oaire:version
Version of Record
Category
学術雑誌論文 Journal Article