Aerobic oxysulfonylation of alkenes using thiophenols: an efficient one-pot route to β-ketosulfones

Abstract

We have developed a highly efficient synthetic route to β-ketosulfones via AgNO3 catalyzed oxysulfonylation of alkenes using thiophenols in the presence of air (O2) and K2S2O8 as eco-friendly oxidants. Thiophenols have been used as sulfonylation precursors for the first time in a dioxygen activation based radical process. Moreover, the protocol also offers a new and convenient method for the synthesis of β-hydroxysulfides at room temperature without the use of any initiator.

Recent advances in sulfur- and phosphorous-centered radical reactions for the formation of S–C and P–C bonds

“…83 The Yadav group reported AgNO 3 -catalyzed oxysulfonylation of alkenes in the presence of air and K 2 S 2 O 8 as oxidants. 84 Sulfenyl radicals generated from thiophenols added to alkenes followed by oxidation with oxygen to from β-hydroxysulfides 72 and then with K 2 S 2 O 8 to form …”

Silver‐Catalyzed Denitrative Sulfonylation of β‐Nitrostyrenes: A Conve­nient Approach to (E)‐Vinyl Sulfones

“…On the basis of the above results and literature precedent,23a,24b,24c a plausible radical addition/elimination mechanism is proposed in Scheme . At first, Ag I triggers the formation of sulfonyl radical 2′ , and the resulting Ag 0 is oxidized to Ag I with the persulfate anion to complete the catalytic cycle.…”

Silver-catalyzed direct spirocyclization of alkynes with thiophenols: a simple and facile approach to 3-thioazaspiro[4,5]trienones

“…No kinetic isotope effects (k H /k D = 1.0) was observed, which indicated C-H bond cleavage might not be the rate-determining 30 step that was similar to mechanisms proposed in previous reports. 11a,14 Based on the above experimental results and previous reports 11a, [14][15][16][17][18] , a postulated reaction pathway was proposed as 35 shown in Scheme 1. Initially, the thiyl radical 4 was generated from thiophenol 2 in the presence of silver salt under air.…”

“…Initially, the thiyl radical 4 was generated from thiophenol 2 in the presence of silver salt under air. 16 Then, the addition of thiyl radical 4 to the triple bond of arylpropiolamide 1 gave vinyl radical 5. Subsequently, the intramolecular spiro-cyclization of vinyl radical 5 with an aryl 40 ring would lead to the formation of the radical intermediate 6.…”