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

Dhiman, Neha; Moustafa, Gamal A. I.; Kasama, Kengo; Aoyama, Hiroshi; Kanomata, Kyohei; Gröger, Harald; Akai, Shuji

doi:https://doi.org/10.1002/cctc.202400932

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

アクセス数:28件（2025-04-10 08:01 集計）

固定URL: https://hdl.handle.net/11094/98130

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タイトル	Dynamic Kinetic Resolution of 2‐Hydroxybiaryl Atropisomers via Lipase‐Catalyzed Enantioselective O‐Acylation
著者	著者名 Dhiman, Neha
	著者名 Moustafa, Gamal A. I.
	NRID 1000040963236 1000040963236 著者名 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 著者名 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 著者名 Kanomata, Kyohei
	著者名 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 著者名 Akai, Shuji
キーワード等	Acylation
	Asymmetric synthesis
	Atropisomerism
	Biaryls
	Density functional calculations
	Dynamic kinetic resolution
	Lipases
内容	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.
抄録	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.
出版者	Wiley
収録物名	ChemCatChem
巻(号)	243
ページ	2904
刊行年月	2024-09-11
言語	英語
ハンドルURL	https://hdl.handle.net/11094/98130
PISSN	18673880
eISSN	18673899
関連情報 (isIdenticalTo)	DOI (出版社版) https://doi.org/10.1002/cctc.202400932
アクセス権	open access
権利情報	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
出版タイプ	Version of Record
カテゴリ	学術雑誌論文 Journal Article

資源タイプ	学術雑誌論文
ローカル資源タイプ	学術雑誌論文
DCTERMS.bibliographicCitation	ChemCatChem. 2024, 243, p. 2904
DC.title	Dynamic Kinetic Resolution of 2‐Hydroxybiaryl Atropisomers via Lipase‐Catalyzed Enantioselective O‐Acylation
DC.creator	Dhiman, Neha
	Moustafa, Gamal A. I.
	Kasama, Kengo
	Aoyama, Hiroshi
	Kanomata, Kyohei
	Gröger, Harald
	Akai, Shuji
DC.publisher	Wiley
DC.language' scheme='DCTERMS.RFC1766	英語
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-09-11
DC.identifier	https://doi.org/10.1002/cctc.202400932
DC.subject	Acylation
	Asymmetric synthesis
	Atropisomerism
	Biaryls
	Density functional calculations
	Dynamic kinetic resolution
	Lipases
DC.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.
DCTERMS.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.
DC.rights	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
DC.format	98130
citation_title	Dynamic Kinetic Resolution of 2‐Hydroxybiaryl Atropisomers via Lipase‐Catalyzed Enantioselective O‐Acylation
citation_author	Dhiman, Neha
	Moustafa, Gamal A. I.
	Kasama, Kengo
	Aoyama, Hiroshi
	Kanomata, Kyohei
	Gröger, Harald
	Akai, Shuji
citation_publisher	Wiley
citation_language	英語
citation_date	2024-09-11
citation_journal_title	ChemCatChem
citation_volume	243
citation_firstpage	2904
citation_doi	https://doi.org/10.1002/cctc.202400932
citation_public_url	https://hdl.handle.net/11094/98130

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

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