A Copper(I)‐Catalyzed Sulfonylative Hiyama Cross‐Coupling

Abstract

An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, where the reductive elimination showcases an usual high energy barrier for a Cu(III)/Cu(I) process.

Experimental and computational insights into the mechanism of the copper(i)-catalysed sulfonylative Suzuki–Miyaura reaction

“…9). 10 For reductive elimination from (DMEDA)Cu(O-SOPh)(Ph)(I), a signicantly higher reductive elimination barrier of +112.5 kJ mol −1 for the O-bound process is suggested than the S-bound value of +36.0 kJ mol −1 .…”

“…This ordering of transmetalation followed by SO 2 binding to the copper(I) centre has also been proposed as a result of the observations by Cantat and colleagues. 10 Through a combination of computational calculations 29 and literature precedent, 30,31 it is strongly believed that this species has a coordination mode of planar h 1 -SO 2 binding through the sulfur atom. This is commonly seen with rst row transition metals.…”

DABSO as a SO2 gas surrogate in the synthesis of organic structures

“…As shown in Scheme 24, a one-pot reaction of aryl iodides, aryl boronic acids, and DABSO leads to the formation of diaryl sulfones in the presence of Cu(I) salt as the catalyst in N,N′-dimethylpropyleneurea (DMPU) as a polar aprotic solvent. 61 In another research study, Ni(II), 62 Ru (II), 63 and Cu(II) [64][65][66] catalytic systems were employed to access similar products.…”

DABSO – A Reagent to Revolutionize Organosulfur Chemistry

“…Cantat and co-workers later developed a sulfonylative Hiyama coupling from triethoxysilanes to prepare biaryl sulfone products (Scheme 16, B). 53 Scheme 16 (A) Cu-catalyzed sulfonylative Suzuki-Miyaura crosscoupling. (B) Cu-catalyzed sulfonylative Hiyama coupling.…”