Amino-assisted synthesis of alkynylthioethers via a visible-light-induced C_(sp)–S^II coupling between bromoalkynes and 2,2′-diaminodiaryldisulfides

Abstract

A straightforward synthesis of alkynylthioethers via an amino-assisted and visible-light-promoted coupling reaction of bromoalkynes with 2,2′-diaminodiphenyldisulfides is developed. The reaction can be accomplished in the absence of transition-metal, photocatalyst and...

Synthesis and Application Dichalcogenides as Radical Reagents with Photochemical Technology

“…Although many synthetic strategies have been established for the C(sp 3 )–S and C(sp 2 )–S bond-forming formation, there are still important challenges for the construction of C(sp)–S bonds, particularly for the achievement of C(sp)–S bond formation [ 84 ]. In 2021, Wang et al reported a strategy for the preparation of alkynyl sulfides using visible-light irradiation ( Scheme 31 ) [ 85 ]. First, 2,2′-diaminodiphenyl disulfides 149 and phenylethynyl bromides 150 were chosen as model substrates, irradiated under blue light, and stirred in CH 2 Cl 2 under an N 2 atmosphere for 12 h to obtain the desired coupling products 151 .…”

Synthesis of Alkynyl Sulfides: Alkynyl Trifluoromethyl Sulfides and Thiocyanates

“…Visible-light-promoted C(sp)À S coupling reaction of 2,2'diaminodiaryldisulfides and bromoalkynes to synthesize alkynyl sulfides was developed by Wang in 2021. [40] Firstly, the authors screened the reaction carefully and gained the optimal conditions as following: a mixture of diaminodiaryldisulfide 4 (0.10 mmol), bromoalkynes 5 (0.10 mmol) in CH 2 Cl 2 under blue LEDs (450-455 nm) at rt for 12 h. Various substances were tolerated under this reaction. In the coupling reaction of diaminodiaryldisulfide, bromoalkynes bearing electron-donating (MeO, Me, tBu) or electron-withdrawing (F, Cl, Br, CN, NO 2 ) groups at phenyl moieties formed the corresponding products (6 b-6 i) in 40-82 % yields.…”

Catalyst-free tandem reaction of 2,2′-diaminodiphenyldisulfides, sulfinic acids and aromatic aldehydes: an approach to synthesize unsymmetric thiosulfonates and benzothiazoles

“…8 However, we found that S-(2-aminophenyl)benzenethiosulfonate (4a) was not produced under visible-light irradiation of a mixture of benzenesulfinic acid (2a) and 2,2′-diaminodiphenyl disulfide (1) in the presence of O 2 (Scheme 1c). Inspired by our recent work on a visible-light induced cascade cyclization involving radicals in a reaction between 2,2′-diaminodiphenyl disulfide and a ketone, 8 we carried out the tandem three-component reaction between 2,2′-diaminodiphenyldisulfide (1), benzenesulfinic acid (2a) and benzaldehyde (3a) in the presence of O 2 and at room temperature (Scheme 1c). To our delight, the reaction afforded (2-aminophenyl)benzenethiosulfonate ( 4a) and 2-phenylbenzothiazole (5a) in good yields.…”

“…Arenesulfinic acids can be easily transformed into sulfonyl radicals in the presence of O 2 7 and 2,2-diaminodiphenyl disulfides can be dissociated under visible light irradiation to generate the free radical o -NH 2 C 6 H 4 S˙. 8 However, we found that S -(2-aminophenyl)benzenethiosulfonate ( 4a ) was not produced under visible-light irradiation of a mixture of benzenesulfinic acid ( 2a ) and 2,2′-diaminodiphenyl disulfide ( 1 ) in the presence of O 2 (Scheme 1c). Inspired by our recent work on a visible-light induced cascade cyclization involving radicals in a reaction between 2,2′-diaminodiphenyl disulfide and a ketone, 8 we carried out the tandem three-component reaction between 2,2′-diaminodiphenyldisulfide ( 1 ), benzenesulfinic acid ( 2a ) and benzaldehyde ( 3a ) in the presence of O 2 and at room temperature (Scheme 1c).…”