open access

https://hdl.handle.net/2115/97572

Photoinduced Direct β-Allylation of Carboxylic Acids Enabled by Boron Catalysis with a Mixed Two-Ligand System

英語

beta-allylation

2025-03-17

Wiley-Blackwell

ChemCatChem

17(11)

A visible-light-induced, boron-catalyzed direct beta-allylation of carboxylic acids with allylsulfones was developed. The selective promotion of beta-allylation over the competing alpha-allylation was achieved by the combined use of a bulky binaphthol derivative and an N-sulfonyl valine derivative as ligands for the boron catalyst. Photoexcitation of catalytically generated diboron ene-1,1-diolates induces single-electron transfer to the allylsulfones, and ensuing deprotonation of the resulting radical cations generates beta-radicals, directing C-C bond formation at the beta-position. The versatility of this catalysis was demonstrated through its application to various pharmaceutical compounds. Furthermore, by leveraging the unique features of the carboxy group preserved in the products, subsequent transformations were successfully achieved, showcasing the capability of the boron catalysis in rapidly increasing the molecular complexity of carboxylic acids.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: K. Sun, Y. Heike, Y. Yoshida, M. Sawamura, D. C.-Y. Huang, Y. Shimizu, Photoinduced Direct β-Allylation of Carboxylic Acids Enabled by Boron Catalysis with a Mixed Two-Ligand System. ChemCatChem 2025, e202500091, which has been published in final form at DOI:10.1002/cctc.202500091. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. 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.

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