02045nas a2200181 4500008004100000022001400041245016200055210006900217260000800286300001400294490000700308520132400315100002501639700002701664700002301691700002601714856012301740 2022 eng d a0022-326300aSolvent-driven mono- and bis-sulfenylation of (E)-beta-iodovinyl sulfones with thiols for flexible synthesis of 1,2-thiosulfonylalkenes and 1,2-dithioalkenes0 aSolventdriven mono and bissulfenylation of Ebetaiodovinyl sulfon cMAR a3934-39510 v873 a

The nature of solvent is a key factor for stereoselective mono-and bis-thiolation of (E)-beta-iodovinyl sulfones with thiols under basic conditions. A novel and unprecedented vicinal bisthiolation of (E)-beta-iodovinyl sulfones with thiols under the influence of K2CO3/DMSO at room temperature for quick assembly of (E)-1,2-dithio-1-alkenes is presented. Solvent-induced stereoselective monosulfenylation of (E)-beta-iodovinyl sulfones with thiols has also been established for the synthesis of both (E)- and (Z)-1,2-thiosulfonylethenes in MeCN and MeOH, respectively. Moreover, K2CO3-mediated desulfonylative-sulfenylation of (Z)-1,2-thiosulfonylethenes with thiols in DMSO furnished unsymmetrical (Z)-1,2-dithio-1-alkenes for the first time. The solvent-dependent versatile reactivity of (E)-beta-iodovinyl sulfones has been successfully explored to provide a set of (E)-/(Z)-1,2-dithio-1-alkenes and (E)-/(Z)-1,2-thiosulfonyl-1-alkenes in good to high yields with excellent stereoselectivities. Notably, this operationally simple process utilizes a broad substrate scope with good functional group tolerance and compatibility. The efficacy of the process has been proven for gram-scale reactions, and plausible mechanistic models are outlined on the basis of experimental results and control experiments.

1 aReddy, Raju, Jannapu1 aKumari, Arram, Haritha1 aSharadha, Nunavath1 aKrishna, Gamidi, Rama uhttps://library.ncl.res.in/content/solvent-driven-mono-and-bis-sulfenylation-e-beta-iodovinyl-sulfones-thiols-flexible