Copper-Catalyzed Regio- And Enantioselective Hydroallylation of 1-Trifluoromethylalkenes: Effect of Crown Ether

Kojima, Yuki; Miura, Masahiro; Hirano, Koji

doi:https://doi.org/10.1021/acscatal.1c02947

Copper-Catalyzed Regio- And Enantioselective Hydroallylation of 1-Trifluoromethylalkenes: Effect of Crown Ether

Kojima, Yuki; Miura, Masahiro; Hirano, Koji

ACS Catalysis, 2021, 11(18), 11663-11670

Number of Access:180（2025-06-08 12:49 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/92695

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Title	Copper-Catalyzed Regio- And Enantioselective Hydroallylation of 1-Trifluoromethylalkenes: Effect of Crown Ether
Creator	CreatorName Kojima, Yuki
	NRID 1000020183626 1000020183626 ORCID 0000-0001-8288-6439 0000-0001-8288-6439 researchmap permalink read0013936 read0013936 Scopus Author ID 7402799909 7402799909 CreatorName Miura, Masahiro
	NRID 1000070532696 1000070532696 ORCID 0000-0001-9752-1985 0000-0001-9752-1985 researchmap permalink koj koj Scopus Author ID 7402407063 7402407063 CreatorName Hirano, Koji
Subject	asymmetric catalysis
	copper
	crown ether
	hydrofunctionalization
	trifluoromethyl group
Description	Kojima Y., Miura M., Hirano K.. Copper-Catalyzed Regio- And Enantioselective Hydroallylation of 1-Trifluoromethylalkenes: Effect of Crown Ether. ACS Catalysis. 11(18), 11663-11670, (2021), 17 September 2021; © 2021 American Chemical Society. https://doi.org/10.1021/acscatal.1c02947.
Abstract	A Cu-catalyzed regio- and enantioselective hydroallylation of 1-trifluoromethylalkenes with hydrosilanes and allylic chlorides has been developed. Anin situgenerated CuH species undergoes the hydrocupration regio- and enantioselectively to form a chiral α-CF3alkylcopper intermediate, which then leads to the optically active hydroallylated product. The key to success is the use of not only an appropriate chiral bisphosphine ligand but also 18-crown-6 to suppress the otherwise predominant β-F elimination from the α-CF3alkylcopper intermediate. The asymmetric Cu catalysis successfully constructs the nonbenzylic and nonallylic CF3-substituted Csp3chiral center, which is difficult to operate by other means.
Publisher	American Chemical Society
Source Title	ACS Catalysis
Volume (Issue)	11(18)
Page	11663-11670
Date of Issued	2021-09-17
Language	English
Handle URL	https://hdl.handle.net/11094/92695
eISSN	21555435
NCID	AA12599706
Relation.isVersionOf	DOI (Publisher Version) https://doi.org/10.1021/acscatal.1c02947
Access Rights	open access
CopyRight	© 2021 American Chemical Society
CopyRight	This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in ACS Catalysis, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acscatal.1c02947.
oaire:version	Accepted Manuscript
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCMI Type	Text
DCTERMS.bibliographicCitation	ACS Catalysis. 2021, 11(18), p. 11663-11670
DC.title	Copper-Catalyzed Regio- And Enantioselective Hydroallylation of 1-Trifluoromethylalkenes: Effect of Crown Ether
DC.creator	Kojima, Yuki
	Miura, Masahiro
	Hirano, Koji
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	English
DC.type' scheme='DCTERMS.DCMIType	Text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2021-09-17
DC.identifier	https://doi.org/10.1021/acscatal.1c02947
DC.subject	asymmetric catalysis
	copper
	crown ether
	hydrofunctionalization
	trifluoromethyl group
DC.description	Kojima Y., Miura M., Hirano K.. Copper-Catalyzed Regio- And Enantioselective Hydroallylation of 1-Trifluoromethylalkenes: Effect of Crown Ether. ACS Catalysis. 11(18), 11663-11670, (2021), 17 September 2021; © 2021 American Chemical Society. https://doi.org/10.1021/acscatal.1c02947.
DCTERMS.abstract	A Cu-catalyzed regio- and enantioselective hydroallylation of 1-trifluoromethylalkenes with hydrosilanes and allylic chlorides has been developed. Anin situgenerated CuH species undergoes the hydrocupration regio- and enantioselectively to form a chiral α-CF3alkylcopper intermediate, which then leads to the optically active hydroallylated product. The key to success is the use of not only an appropriate chiral bisphosphine ligand but also 18-crown-6 to suppress the otherwise predominant β-F elimination from the α-CF3alkylcopper intermediate. The asymmetric Cu catalysis successfully constructs the nonbenzylic and nonallylic CF3-substituted Csp3chiral center, which is difficult to operate by other means.
DC.rights	© 2021 American Chemical Society
DC.rights	This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in ACS Catalysis, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acscatal.1c02947.
DC.format	92695
citation_title	Copper-Catalyzed Regio- And Enantioselective Hydroallylation of 1-Trifluoromethylalkenes: Effect of Crown Ether
citation_author	Kojima, Yuki
	Miura, Masahiro
	Hirano, Koji
citation_publisher	American Chemical Society
citation_language	English
citation_date	2021-09-17
citation_journal_title	ACS Catalysis
citation_volume	11
citation_issue	18
citation_firstpage	11663
citation_lastpage	11670
citation_doi	https://doi.org/10.1021/acscatal.1c02947
citation_public_url	https://hdl.handle.net/11094/92695

Copper-Catalyzed Regio- And Enantioselective Hydroallylation of 1-Trifluoromethylalkenes: Effect of Crown Ether

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