摘要：RyuseiOhkura, YasuyoTahara-Tezuka, Daisuke Yokogawa, Cathleen M. Crudden,* and Masakazu Nambo*

转自：康龙化成

Desulfonylative Suzuki–Miyaura Cross-Coupling of Unactivated Aryl Sulfones through Ni Catalysis

Ryusei Ohkura, Yasuyo Tahara-Tezuka, Daisuke Yokogawa, Cathleen M. Crudden,* and Masakazu Nambo*

Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Nagoya 464-8602, Japan;

Department of Chemistry, Queen’s University, Kingston, Ontario K7L 3N6, Canada

Carbon to Metal Coating Institute, Queen’s University, Kingston, Ontario K7L3N6, Canada

—ACS Catal., 2025, doi.org/10.1021/acscatal.5c02609.

Recommended by Shi Li_MOC and Yuting Gao_MC3

KEYWORDS: Suzuki coupling, Desulfonylation, Nicatalysis(反应类型), C(sp2)-C(sp2) (成键类型), aryl sulfones, arylboroxines (原料), biaryls (产物)

ABSTRACT: We describe a Ni-catalyzed Suzuki–Miyaura cross-coupling of simple aryl sulfones with arylboroxines through carbon–sulfonyl (C–SO2) bond activation. The use of 1,5-cyclooctadiene (cod) as a ligand on Ni is essential in this cross-coupling reaction, affording unsymmetric biarylproducts in good yields. The utilization of the sulfonyl moiety as both an electron-withdrawing and directing group provides highly functionalized products via regioselective and iterative transformations, which are difficult to achieve with typical leaving groups, such as aryl halides. Moreover, cyclic aryl sulfones can be employed in ring-opening cross-coupling and subsequent trapping reactions with various electrophiles, producing π-conjugated structures bearing valuable, sulfur-containing functional groups. Competition experiments reveal that the Ni-cod catalyst preferentially promotes the coupling with aryl sulfones over aryl chlorides, which is opposite the conventional reactivity of aryl electrophiles. Additionally, the sodium sulfinate released during C–SO2 bond cleavage exhibits an unprecedented rate-accelerating effect, which is supported by mechanistic studies, control experiments and density functional theory (DFT) calculations.

Introduction

Reaction Condition Optimization

Substrate Scope (selected examples)

Ni-Catalyzed Ring-Opening Cross-Coupling of Cyclic Aryl Sulfonesa

Iterative Transformations of Aryl Sulfones

Ohkura et al. reported a Ni-catalyzed Suzuki–Miyaura cross-coupling of unactivated aryl sulfones via selective activation of the carbon–sulfonyl (C–SO₂) bond. The transformation efficiently constructs unsymmetric biaryl scaffolds from simple sulfone substrates and arylboroxines, with broad substrate scope and good functional group tolerance. Notably, the sulfonyl group serves as both a leaving and directing group, enabling iterative coupling and ring-opening strategies for cyclic sulfones. Mechanistic and DFT studies revealed the unique rate-accelerating role of in situ formed sodium sulfinate and the crucial influence of cod ligands on Ni. This work provides a rare example of sulfone-selective activation over aryl halides and expands the synthetic utility of sulfones in cross-coupling chemistry.

来源：新浪财经