Axial chirality around N-P bonds induced by complexation between E(C6F5)3 (E = B, Al) and an N-phosphine oxide-substituted imidazolinylidene: A key intermediate in the catalytic phosphinoylation of CO2

Asada, Takahiro; Hoshimoto, Yoichi; Kawakita, Takahiro; Kinoshita, Takuya; Ogoshi, Sensuke

doi:https://doi.org/10.1021/acs.joc.9b03210

Axial chirality around N-P bonds induced by complexation between E(C6F5)3 (E = B, Al) and an N-phosphine oxide-substituted imidazolinylidene: A key intermediate in the catalytic phosphinoylation of CO2

Asada, Takahiro; Hoshimoto, Yoichi; Kawakita, Takahiro et al.

Journal of Organic Chemistry, 2020, 85(22), 14333-14341

Number of Access:580（2025-07-26 12:17 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/92550

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Title	Axial chirality around N-P bonds induced by complexation between E(C6F5)3 (E = B, Al) and an N-phosphine oxide-substituted imidazolinylidene: A key intermediate in the catalytic phosphinoylation of CO2
Creator	CreatorName Asada, Takahiro
	NRID 1000030710074 1000030710074 ORCID 0000-0003-0882-6109 0000-0003-0882-6109 researchmap permalink YHoshimoto YHoshimoto Scopus Author ID 36463455400 36463455400 CreatorName Hoshimoto, Yoichi
	CreatorName Kawakita, Takahiro
	CreatorName Kinoshita, Takuya
	NRID 1000030252589 1000030252589 researchmap permalink read0042792 read0042792 Scopus Author ID 7005303403 7005303403 CreatorName Ogoshi, Sensuke
Subject	Carbene compounds
	Chirality
	Complexation
	Molecular structure
	Nuclear magnetic resonance spectroscopy
Description	Asada T., Hoshimoto Y., Kawakita T., et al. Axial chirality around N-P bonds induced by complexation between E(C6F5)3 (E = B, Al) and an N-phosphine oxide-substituted imidazolinylidene: A key intermediate in the catalytic phosphinoylation of CO2. Journal of Organic Chemistry 85, 14333 (2020); https://doi.org/10.1021/acs.joc.9b03210.
Abstract	Complexation-induced axial chirality around an N-P bond occurs upon the predominant coordination of the N-phosphinoyl group in the N-phosphine oxide-substituted imidazolinylidene (SPoxIm) to B(C6F5)3. (Ra) and (Sa) atropisomers of (κ-O-SPoxIm)B(C6F5)3 were observed independently in the single-crystal lattice and the optimized gas-phase structure. Experimental and theoretical studies confirmed that this axial chirality arises from the restricted rotation around the N-P bond, caused by the steric repulsion between the C5-H atoms of the imidazolinylidene ring and the C6F5 rings on the B(C6F5)3 unit. Conversely, this axial chirality was not certainly observed via the complexation between SPoxIm and Al(C6F5)3. The carbene carbon atoms in (κ-O-SPoxIm)E(C6F5)3 (E = B, Al) remain sufficiently nucleophilic to react with CO2, and the phosphinoylation of CO2 with SPoxIm proceeds far more rapidly in the presence of a catalytic amount of Al(C6F5)3 than in the absence of Al(C6F5)3
Publisher	American Chemical Society
Source Title	Journal of Organic Chemistry
Volume (Issue)	85(22)
Page	14333-14341
Date of Issued	2020-11-20
Language	English
Handle URL	https://hdl.handle.net/11094/92550
PISSN	00223263
eISSN	15206904
NCID	AA12097242
Relation.isIdenticalTo	DOI (Publisher Version) https://doi.org/10.1021/acs.joc.9b03210
Access Rights	open access
CopyRight	© 2022 American Chemical Society
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

Resource Type	journal article
Local Type	Journal Article
DCMI Type	Text
DCTERMS.bibliographicCitation	Journal of Organic Chemistry. 2020, 85(22), p. 14333-14341
DC.title	Axial chirality around N-P bonds induced by complexation between E(C6F5)3 (E = B, Al) and an N-phosphine oxide-substituted imidazolinylidene: A key intermediate in the catalytic phosphinoylation of CO2
DC.creator	Asada, Takahiro
	Hoshimoto, Yoichi
	Kawakita, Takahiro
	Kinoshita, Takuya
	Ogoshi, Sensuke
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	English
DC.type' scheme='DCTERMS.DCMIType	Text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2020-11-20
DC.identifier	https://doi.org/10.1021/acs.joc.9b03210
DC.subject	Carbene compounds
	Chirality
	Complexation
	Molecular structure
	Nuclear magnetic resonance spectroscopy
DC.description	Asada T., Hoshimoto Y., Kawakita T., et al. Axial chirality around N-P bonds induced by complexation between E(C6F5)3 (E = B, Al) and an N-phosphine oxide-substituted imidazolinylidene: A key intermediate in the catalytic phosphinoylation of CO2. Journal of Organic Chemistry 85, 14333 (2020); https://doi.org/10.1021/acs.joc.9b03210.
DCTERMS.abstract	Complexation-induced axial chirality around an N-P bond occurs upon the predominant coordination of the N-phosphinoyl group in the N-phosphine oxide-substituted imidazolinylidene (SPoxIm) to B(C6F5)3. (Ra) and (Sa) atropisomers of (κ-O-SPoxIm)B(C6F5)3 were observed independently in the single-crystal lattice and the optimized gas-phase structure. Experimental and theoretical studies confirmed that this axial chirality arises from the restricted rotation around the N-P bond, caused by the steric repulsion between the C5-H atoms of the imidazolinylidene ring and the C6F5 rings on the B(C6F5)3 unit. Conversely, this axial chirality was not certainly observed via the complexation between SPoxIm and Al(C6F5)3. The carbene carbon atoms in (κ-O-SPoxIm)E(C6F5)3 (E = B, Al) remain sufficiently nucleophilic to react with CO2, and the phosphinoylation of CO2 with SPoxIm proceeds far more rapidly in the presence of a catalytic amount of Al(C6F5)3 than in the absence of Al(C6F5)3
DC.rights	© 2022 American Chemical Society
DC.rights	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
DC.format	92550
citation_title	Axial chirality around N-P bonds induced by complexation between E(C6F5)3 (E = B, Al) and an N-phosphine oxide-substituted imidazolinylidene: A key intermediate in the catalytic phosphinoylation of CO2
citation_author	Asada, Takahiro
	Hoshimoto, Yoichi
	Kawakita, Takahiro
	Kinoshita, Takuya
	Ogoshi, Sensuke
citation_publisher	American Chemical Society
citation_language	English
citation_date	2020-11-20
citation_journal_title	Journal of Organic Chemistry
citation_volume	85
citation_issue	22
citation_firstpage	14333
citation_lastpage	14341
citation_doi	https://doi.org/10.1021/acs.joc.9b03210
citation_public_url	https://hdl.handle.net/11094/92550

Axial chirality around N-P bonds induced by complexation between E(C6F5)3 (E = B, Al) and an N-phosphine oxide-substituted imidazolinylidene: A key intermediate in the catalytic phosphinoylation of CO2

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