Theoretical Investigation on the Copper‐Catalyzed anti‐Selective 1,2‐Silylboration of Internal Alkynes

Moniwa, Hirokazu; Yamanaka, Masahiro; Shintani, Ryo

doi:https://doi.org/10.1002/ejoc.202401155

Theoretical Investigation on the Copper‐Catalyzed anti‐Selective 1,2‐Silylboration of Internal Alkynes

Moniwa, Hirokazu; Yamanaka, Masahiro; Shintani, Ryo

European Journal of Organic Chemistry, 2025, e202401155

アクセス数:230件（2025-08-28 22:25 集計）

固定URL: https://hdl.handle.net/11094/100402

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タイトル	Theoretical Investigation on the Copper‐Catalyzed anti‐Selective 1,2‐Silylboration of Internal Alkynes
著者	著者名 Moniwa, Hirokazu
	NRID 1000060343167 1000060343167 著者名 Yamanaka, Masahiro
	NRID 1000050372561 1000050372561 researchmap permalink RMshintani RMshintani Scopus Author ID 6701562981 6701562981 著者名 Shintani, Ryo
キーワード等	alkyne
	copper
	DFT calculation
	mechanism
	silylboronate
内容	This is the peer reviewed version of the following article: Moniwa Hirokazu, Yamanaka Masahiro, Shintani Ryo. Theoretical Investigation on the Copper‐Catalyzed anti‐Selective 1,2‐Silylboration of Internal Alkynes. European Journal of Organic Chemistry, e202401155 (2025), which has been published in final form at https://doi.org/10.1002/ejoc.202401155. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
抄録	The mechanism of a copper-catalyzed regio- and anti-selective 1,2-silylboration of internal alkynes was theoretically studied to understand the reaction pathway and the origin of selectivity. The proposed overall reaction pathway involves the syn-to-anti isomerization via an anionic allenic transition state stabilized by the conjugation with the benzene ring. The anti-selectivity is determined at the borylation step and controlled by the steric effect of the silyl group introduced on the alkyne carbon. The computational results obtained in this study are highly informative for the development of new catalytic transformations involving syn/anti-isomerization processes.
出版者	Wiley
収録物名	European Journal of Organic Chemistry
ページ	e202401155
刊行年月	2025-01-10
言語	英語
ハンドルURL	https://hdl.handle.net/11094/100402
PISSN	1434193X
eISSN	10990690
関連情報 (isVersionOf)	DOI (出版社版) https://doi.org/10.1002/ejoc.202401155
アクセス権	embargoed access
権利情報	© 2025 Wiley-VCH GmbH
権利情報	The full-text file will be made open to the public on 10 January 2026 in accordance with the publisher's policy.
出版タイプ	Accepted Manuscript
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	European Journal of Organic Chemistry. 2025, p. e202401155
DC.title	Theoretical Investigation on the Copper‐Catalyzed anti‐Selective 1,2‐Silylboration of Internal Alkynes
DC.creator	Moniwa, Hirokazu
	Yamanaka, Masahiro
	Shintani, Ryo
DC.publisher	Wiley
DC.language' scheme='DCTERMS.RFC1766	英語
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2025-01-10
DC.identifier	https://doi.org/10.1002/ejoc.202401155
DC.subject	alkyne
	copper
	DFT calculation
	mechanism
	silylboronate
DC.description	This is the peer reviewed version of the following article: Moniwa Hirokazu, Yamanaka Masahiro, Shintani Ryo. Theoretical Investigation on the Copper‐Catalyzed anti‐Selective 1,2‐Silylboration of Internal Alkynes. European Journal of Organic Chemistry, e202401155 (2025), which has been published in final form at https://doi.org/10.1002/ejoc.202401155. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
DCTERMS.abstract	The mechanism of a copper-catalyzed regio- and anti-selective 1,2-silylboration of internal alkynes was theoretically studied to understand the reaction pathway and the origin of selectivity. The proposed overall reaction pathway involves the syn-to-anti isomerization via an anionic allenic transition state stabilized by the conjugation with the benzene ring. The anti-selectivity is determined at the borylation step and controlled by the steric effect of the silyl group introduced on the alkyne carbon. The computational results obtained in this study are highly informative for the development of new catalytic transformations involving syn/anti-isomerization processes.
DC.rights	© 2025 Wiley-VCH GmbH
DC.rights	The full-text file will be made open to the public on 10 January 2026 in accordance with the publisher's policy.
DC.format	100402
citation_title	Theoretical Investigation on the Copper‐Catalyzed anti‐Selective 1,2‐Silylboration of Internal Alkynes
citation_author	Moniwa, Hirokazu
	Yamanaka, Masahiro
	Shintani, Ryo
citation_publisher	Wiley
citation_language	英語
citation_date	2025-01-10
citation_journal_title	European Journal of Organic Chemistry
citation_firstpage	e202401155
citation_doi	https://doi.org/10.1002/ejoc.202401155
citation_public_url	https://hdl.handle.net/11094/100402

Theoretical Investigation on the Copper‐Catalyzed anti‐Selective 1,2‐Silylboration of Internal Alkynes

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