Stable BF$_2$ boracycles as versatile reagents for selective ortho C–H functionalization

Shinde, Ganesh (author), Babiker, Jonatan (author), Mebrahtu, Michelle (author), Prigent, Anaïs (author), Foucras, Gauthier (author), Aher, Yogesh N. (author), Amombo Noa, Francoise M. (author), Johansson, Magnus J. (author), Košmrlj, Janez (author), Jansen-van Vuuren, Ross D. (author), Cailly, Thomas (author), Sundén, Henrik (author)

The development of new boron reagents continues to play a crucial role in advancing modern organic synthesis, particularly in C–H functionalization and cross-coupling reactions. Herein, we report a metal-free, robust, and scalable multigram protocol for the synthesis of stable BF$_2$ boracycles that require no column chromatography, providing a practical and efficient route to access this valuable boron species. The BF$_2$ boracycles exhibit enhanced stability and reactivity, making them highly versatile intermediates for late-stage diversification. They undergo ipso-substitution to afford a wide array of derivatives, including halogenated (e.g., radioiodinated), hydroxylated, and azidated products. Furthermore, they display excellent reactivity in Suzuki–Miyaura cross-coupling reactions, enabling both C(sp$^2$)─C(sp$^2$) and C(sp$^2$)─C(sp$^3$) bond formation. These results underscore the utility of BF$_2$ boracycles as powerful tools for selective functionalization in pharmaceutical synthesis and beyond. Our work represents a significant advancement in organoboron chemistry, offering both a streamlined synthetic approach and broad applicability for complex molecule construction.

• Language: English
• Keywords: boracycle, ortho functionalization, ipso substitution, pivalamide, radioiodination, O-carbamates, phenols, multigram scale
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Publication status: Published
• Publication version: Version of Record
• Year: 2026
• Number of pages: 9 str.
• Numbering: Vol. 65, iss. 8, art. e18421
• PID: 20.500.12556/RUL-181101
• UDC: 547.1.057:546.27
• ISSN on article: 1433-7851
• DOI: 10.1002/anie.202518421
• COBISS.SI-ID: 265701123
• Publication date in RUL: 25.03.2026

Record is a part of a journal

• Title: Angewandte Chemie : International edition
• Shortened title: Angew. Chem.
• Publisher: Wiley-VCH
• ISSN: 1433-7851
• COBISS.SI-ID: 18592005

Licences

• License: CC BY 4.0, Creative Commons Attribution 4.0 International
• Link: http://creativecommons.org/licenses/by/4.0/
• Description: This is the standard Creative Commons license that gives others maximum freedom to do what they want with the work as long as they credit the author.

Secondary language

• Language: Slovenian
• Keywords: boracikel, orto funkcionalizacija, ipso substitucija, pivalamid, radiojodiranje, O-karbamati, fenoli, multigramska lestvica