Lipase‐Palladium Co‐catalyzed Dynamic Kinetic Resolution of Racemic Allylic Esters

Oono, Masato; Yamada, Akane; Kimura, Masanari; Kanomata, Kyohei; Akai, Shuji

doi:https://doi.org/10.1002/chem.202404406

Lipase‐Palladium Co‐catalyzed Dynamic Kinetic Resolution of Racemic Allylic Esters

Oono, Masato; Yamada, Akane; Kimura, Masanari et al.

Chemistry – A European Journal, 2025, e202404406

Number of Access:576（2025-08-17 20:38 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/100631

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Title	Lipase‐Palladium Co‐catalyzed Dynamic Kinetic Resolution of Racemic Allylic Esters
Creator	CreatorName Oono, Masato
	CreatorName Yamada, Akane
	NRID 1000010274622 1000010274622 CreatorName Kimura, Masanari
	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
	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
Description	This is the accepted version of the following article: Oono Masato, Yamada Akane, Kimura Masanari, et al. Lipase‐Palladium Co‐catalyzed Dynamic Kinetic Resolution of Racemic Allylic Esters. Chemistry – A European Journal, e202404406, which has been published in final form at https://doi.org/10.1002/chem.202404406. This article may be used for non-commercialpurposes in accordance with the Wiley Self-ArchivingPolicy [https://authorservices.wiley.com/author-resources/Journal-Authors/licensing/self-archiving.html]
Abstract	Dynamic kinetic resolution (DKR) by combining lipase-catalyzed esterification of racemic sec-alcohols and in situ racemization has been widely studied; however, reports on DKR involving lipase-catalyzed hydrolysis of racemic esters are scarce. This problem is probably due to the lack of more effective and general racemization methods. Herein, we report the enhanced hydrolytic DKR of racemic allylic esters. The discovery of the monodentate ligand P[C6H3-2,6-(OMe)2]3, which in situ generates Pd complex(es) highly reactive to racemization and the NaOAc-mediated acceleration of racemization, are notable breakthroughs. Consequently, the DKR of racemic allylic esters can be completed in a few hours at 40 °C in most cases, yielding optically active allylic alcohols (93% to >99% ee) in 58%–91% isolated yields with minimal side reactions.
Publisher	Wiley
Source Title	Chemistry – A European Journal
Page	e202404406
Date of Issued	2025-03-13
Language	English
Handle URL	https://hdl.handle.net/11094/100631
PISSN	09476539
eISSN	15213765
Relation.isVersionOf	DOI (Publisher Version) https://doi.org/10.1002/chem.202404406
Access Rights	embargoed access
CopyRight	© 2025 Wiley-VCH GmbH
CopyRight	The full-text file will be made open to the public on 13 March 2026 in accordance with the publisher's policy.
oaire:version	Accepted Manuscript
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCTERMS.bibliographicCitation	Chemistry – A European Journal. 2025, p. e202404406
DC.title	Lipase‐Palladium Co‐catalyzed Dynamic Kinetic Resolution of Racemic Allylic Esters
DC.creator	Oono, Masato
	Yamada, Akane
	Kimura, Masanari
	Kanomata, Kyohei
	Akai, Shuji
DC.publisher	Wiley
DC.language' scheme='DCTERMS.RFC1766	English
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2025-03-13
DC.identifier	https://doi.org/10.1002/chem.202404406
DC.description	This is the accepted version of the following article: Oono Masato, Yamada Akane, Kimura Masanari, et al. Lipase‐Palladium Co‐catalyzed Dynamic Kinetic Resolution of Racemic Allylic Esters. Chemistry – A European Journal, e202404406, which has been published in final form at https://doi.org/10.1002/chem.202404406. This article may be used for non-commercialpurposes in accordance with the Wiley Self-ArchivingPolicy [https://authorservices.wiley.com/author-resources/Journal-Authors/licensing/self-archiving.html]
DCTERMS.abstract	Dynamic kinetic resolution (DKR) by combining lipase-catalyzed esterification of racemic sec-alcohols and in situ racemization has been widely studied; however, reports on DKR involving lipase-catalyzed hydrolysis of racemic esters are scarce. This problem is probably due to the lack of more effective and general racemization methods. Herein, we report the enhanced hydrolytic DKR of racemic allylic esters. The discovery of the monodentate ligand P[C6H3-2,6-(OMe)2]3, which in situ generates Pd complex(es) highly reactive to racemization and the NaOAc-mediated acceleration of racemization, are notable breakthroughs. Consequently, the DKR of racemic allylic esters can be completed in a few hours at 40 °C in most cases, yielding optically active allylic alcohols (93% to >99% ee) in 58%–91% isolated yields with minimal side reactions.
DC.rights	© 2025 Wiley-VCH GmbH
DC.rights	The full-text file will be made open to the public on 13 March 2026 in accordance with the publisher's policy.
DC.format	100631
citation_title	Lipase‐Palladium Co‐catalyzed Dynamic Kinetic Resolution of Racemic Allylic Esters
citation_author	Oono, Masato
	Yamada, Akane
	Kimura, Masanari
	Kanomata, Kyohei
	Akai, Shuji
citation_publisher	Wiley
citation_language	English
citation_date	2025-03-13
citation_journal_title	Chemistry – A European Journal
citation_firstpage	e202404406
citation_doi	https://doi.org/10.1002/chem.202404406
citation_public_url	https://hdl.handle.net/11094/100631

Lipase‐Palladium Co‐catalyzed Dynamic Kinetic Resolution of Racemic Allylic Esters

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