Pd(OAc)₂/PPh₃‐Catalyzed Desulfonylative Homocoupling of Arylsulfonyl Chlorides

Abstract

The Pd-catalyzed homodimerization with respect to arylsulfonyl chlorides as an efficient method for the synthesis of biaryls has been developed. This desulfonylative reaction which was performed at reflux in 1,4-dioxane for 4 h under air afforded the desired products in good to excellent yields.

Visible Light-Driven, Gold(I)-Catalyzed Preparation of Symmetrical (Hetero)biaryls by Homocoupling of Arylazo Sulfones

“…Spectroscopic data were in accordance with the literature data. 48 1 H NMR (300 MHz, CDCl 3 ) δ 7.48–7.39 (m, 2H), 7.33 (d, J = 7.2 Hz, 2H), 7.28–7.15 (m, 4H), 2.41 (s, 6H). 13 C{ 1 H} NMR (75 MHz, CDCl 3 ) δ 138.5, 137.8, 129.7, 128.2, 124.7, 124.2, 15.4.…”

“…Spectroscopic data were in accordance with literature data. 48 1 H NMR (300 MHz, CDCl 3 ) δ 7.72 (t, J = 1.9 Hz, 1H), 7.51 (ddt, J = 9.7, 7.9, 1.1 Hz, 2H), 7.35 (d, J = 7.9 Hz, 1H). 13 C{ 1 H} NMR (75 MHz, CDCl 3 ) δ 141.9, 131.0, 130.5, 130.3, 125.9, 123.1.…”

Copper-Free Palladium-Catalysed Desulfinative Homocoupling of Sodium Arylsulfinates under Mild and Aerobic Conditions

“…When benzoyl peroxide (BPO) was used as an oxidant (see SAFETY WARNING in Experimental section), we were pleased to find that biphenyl was obtained in 56% yield without the detection of any diphenyl sulfone byproduct (Table 2, entry 11). Other peroxides, such as tert-butyl peroxyacetate (TBPA), tert-butyl peroxybenzoate (TBPB), and tert-butyl peroxypivalate (TBPV) were significantly more effective, whereas di-tert-amyl peroxide (DTAP) and tertamyl hydroperoxide (TAHP) gave comparable results (Table 2, entries [12][13][14][15][16]. tert-Butyl cumyl peroxide (TBCP) and dicumyl peroxide (DCP) were ineffective for the generation of 1a (Table 2, entries 17 and 18).…”

“…Inspired by the homocoupling reaction of aryl halides, [6][7] alternative approaches to the synthesis of biaryls, involving homocoupling of aryl metal reagents, [8][9] dimerisation of organoborane reagents [10][11] and decarboxylative dimerisation of aryl carboxylic acids 12 as well as desulfinative homocoupling of aryl sulfonyl compounds have been developed. [13][14][15] However, the homocoupling of arylsulfinic acid salts has not been wellestablished yet.…”

Palladium‐catalyzed reductive homocoupling of aryl sulfonates via cleavage of C─O bond at room temperature

“…Decarboxylative dimerization of arylcarboxylic acids was reported by Cornella et al with limited substrate universality under harsh conditions (Scheme , C─C cleavage). Desulfitative homocoupling of arylsulfonyl compounds has drawn much attention for their higher reactivities under milder conditions than corresponding arylcarboxylic acids (Scheme , C─S cleavage) . However, the generation of environmentally detrimental sulfur dioxide was unavoidable.…”