康 · 学术 | Reaction of the Day No. 1753

Integration of Proximal Alkoxide and Lewis Acidic Cations To Boost Nickel-Catalyzed Borylation

Benjamin S. Grills, Jennifer A. Garden, and Benjamin N. Bhawal*

School of Chemistry, The University of Edinburgh, Edinburgh EH9 3FJ, U.K.

—Org. Lett.,2026, 28(4),1436-1440.

Recommended by Shi Li _ MOC

KEYWORDS: Ni catalysis, borylation (反应类型), aryl chlorides, B2Pin2(原料), boronates, borylated products (产物), C(sp2)-B (成键类型), (n-Bu)2Mg,KHMDS (其它) 

ABSTRACT: Nickel catalysis offers a sustainable alternative to palladium catalysis for cross-coupling reactions, yet ligands tailored for nickel catalysis are lacking. The authors introduce new phosphine ligands designed to facilitate the incorporation of Lewis acidic cations. The combination of a phosphinoalcohol ligand with either (n-Bu)2Mg or KHMDS, as a source of Mg2+ or K+ cations respectively, proved to be optimal for the borylation of aryl chlorides. Studies verified that incorporation of Lewis acidic cations in the proximity of the Ni center enhances reactivity.

Background and This Work

Evaluation of Ligands and Organometallic Bases for the Borylation of 1a

Experiments to Probe the Impact of Ligand Design

Substrate Scope

Proposed Mechanism

Summary and Comments

Prof. Benjamin N. Bhawal et al. developed new phosphine ligands that enable the incorporation of proximal Lewis acidic cations and an alkoxide functionality for the Ni-catalyzed borylation of aryl chlorides. Studies using analogues of phosphinoalcohol ligand L2 verified the formation of a metal alkoxide complex and the fact that incorporation of a Lewis acidic cation and alkoxide within the Ni complex enhances reactivity. This introduces a new opportunity for ligand design in Ni catalysis and should serve as inspiration for future ligand design strategies.

Prof. Benjamin N. Bhawal等人开发了新型膦配体，通过邻位路易斯酸阳离子与醇盐官能团的引入，实现了镍催化芳基氯化物的硼化反应。使用磷烷基醇配体L2类似物进行的研究证实了金属醇盐复合物的形成，并表明在Ni配合物中引入路易斯酸阳离子和醇盐能够显著提高反应活性。这一发现为镍催化中配体的设计提供了新的机遇，也为未来配体设计策略提供了灵感。