Visible light-initiated manganese-catalyzed hydrosulfonylation of alkenes

Abstract

Strategies for the preparation of sulfones have received much attention because they have found widespread applications in the areas of pharmaceutical, agrochemical, and material sciences. Although the radical hydrosulfonylations of...

Regio- and stereoselective manganese-catalyzed hydrosulfonylation of alkynes: facile access to Z-vinyl sulfones

“…Based on our mechanistic studies as well as previous disclosures, 19–21 we proposed a possible reaction mechanism, which is depicted in Scheme 5. Under irradiation by white light, L1 Mn(CO) 3 ˙ ( I ) is generated from the homolysis of L1 2 Mn 2 (CO) 6 , which is formed in situ from Mn 2 (CO) 10 and the ligand ( L1 ) (see ESI Fig.…”

“…Based on our mechanistic studies as well as previous disclosures, [19][20][21] we proposed a possible reaction mechanism, which is depicted in Scheme 5. Under irradiation by white light, L1Mn(CO) 3…”

“…Herein, we disclose the successful realization of a radical alkyne hydrosulfonylation by merging the manganese catalyst and a common bidentate phosphine ligand. 21 Our method is characterized by its mild reaction conditions, excellent regio- and Z -stereoselectivity profile, and broad substrate scope, providing rapid, reliable, and modular access to structurally diverse aliphatic ( Z )-vinyl sulfones.…”

Light-promoted photocatalyst-free and redox-neutral hydrosulfonylation of unactivated alkenes using sulfinic acid

“…Taking advantage of the green and efficient photochemical strategies, significant progress is being achieved in the synthesis of alkyl-substituted sulfones. Sulfonyl chlorides, 9–13 sulfinate salts, 14–17 sulfonamides, 18,19 tetrazole sulfones 20 and a mixture of DABCO·(SO 2 ) 2 and alkyl Hantzsch ester 21 have been employed as sulfonyl radical precursors in the anti-Markovnikov addition reaction to feedstock alkenes (Scheme 2). The Gouverneur group reported the elegant use of commercially available sulfonyl chlorides for photoredox-catalyzed hydrosulfonylation; however, external hydrogen atom donors such as tris(trimethylsilyl)silane are essential.…”

Multicomponent hydrosulfonylation of alkynes for the synthesis of vinyl sulfones

“…Moreover, a radical clock experiment with (1-cyclopropylvinyl)benzene 6a under the standard conditions exclusively furnished the ring-opened product 7a in 79% yield and the coupling product 8a in 82% yield, which demonstrated the intermediacy of the sulfonyl radical and demonstrated that 4-(trifluoromethyl)benzenethiol was the source of hydrogen in this transformation (Scheme 2b). 15 Lastly, deuterium labeling experiments were performed (Scheme 2c): (1) use of D 2 O under the standard conditions afforded the mixed H/D product in 84% yield (27% of D); and (2) including D 2 O without 4-(trifluoromethyl)benzenethiol in the reaction did not work. In addition, when only 4a was reacted in D 2 O, no deuterated product was detected.…”