Issue 42, 2024

A silylboronate-mediated strategy for cross-coupling of alkyl fluorides with aryl alkanes: mechanistic insights and scope expansion

Abstract

The construction of C(sp3)–C(sp3) bonds is pivotal in organic synthesis; however, traditional methods involving alkyl halides are often limited by substrate tolerance and bond dissociation energies, particularly with alkyl fluorides. Herein, we report a silylboronate-mediated cross-coupling strategy that circumvents these challenges, enabling the efficient formation of C(sp3)–C(sp3) bonds between alkyl fluorides and aryl alkanes under mild conditions. Various alkyl fluorides have also been effectively utilized, demonstrating the versatility and broad applicability of this approach. The use of diglyme is critical for this transformation which encapsulates potassium cations and enhances the reaction efficiency. Conventional alkyl halides, including chlorides, bromides, and iodides, are also suitable for this transformation. Density functional theory (DFT) calculations were conducted on the silylboronate-mediated coupling reactions for the first time. Interestingly, while experimental results suggest a radical mechanism, DFT calculations indicate a preference for an ionic pathway.

Graphical abstract: A silylboronate-mediated strategy for cross-coupling of alkyl fluorides with aryl alkanes: mechanistic insights and scope expansion

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Article information

Article type
Edge Article
Submitted
02 Jul 2024
Accepted
23 Sep 2024
First published
01 Oct 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 17418-17424

A silylboronate-mediated strategy for cross-coupling of alkyl fluorides with aryl alkanes: mechanistic insights and scope expansion

J. Zhou, Z. Zhao, T. Kiyono, A. Matsuno, J. Escorihuela and N. Shibata, Chem. Sci., 2024, 15, 17418 DOI: 10.1039/D4SC04357J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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