Atom Transfer Radical Addition to Styrenes with Thiosulfonates Enabled by Synergetic Copper/Photoredox Catalysis

Photocatalyzed Thiosulfonylation of Sila-enynes with Thiosulfonates

“…Among them, Cu(I)/photoredox catalyzedthiosulfonylation of terminal alkenes with thiosulfonates has been achieved to regioselectively assemble sulfonylethyl thioethers, in which thiyl group and arylsulfonyl moiety were incorporated at the C1-and C2-position of alkenes, respectively (Scheme 1a). 19 By contrast, Au(I)/photoredox-catalyzed 2,6-or 1,6-thiosulfonylation of enynes with thiosulfonates developed by Xu could regioselectively install a sulfonyl group at the C1-position or C2-position of alkynes (Scheme 1b). 20 These works encouraged us to expect that the silyl hyperconjugation effect could possibly induce sulfonyl radicals to regioselectively attack vinyl moiety of orthoalkynylaryl vinylsilanes by delicately controlling the photocatalysis system, then followed by cascade coupling-cyclization with alkynes and thiyl moiety to switch the regioselectivity of enyne thiosulfonylation, furnishing thiosulfone-bifunctionalized silacycle skeletons (Scheme 1c).…”

“…Nevertheless, thiosulfonates have been recently reported to act as environment-benign sulfurizing reagents to allow for the regioselective functionalization of arenes, alkenes, allenes, and alkynes, respectively. Among them, Cu­(I)/photoredox catalyzed-thiosulfonylation of terminal alkenes with thiosulfonates has been achieved to regioselectively assemble sulfonylethyl thioethers, in which thiyl group and arylsulfonyl moiety were incorporated at the C1- and C2-position of alkenes, respectively (Scheme a) . By contrast, Au­(I)/photoredox-catalyzed 2,6- or 1,6-thiosulfonylation of enynes with thiosulfonates developed by Xu could regioselectively install a sulfonyl group at the C1-position or C2-position of alkynes (Scheme b) .…”

The Synthesis of (E)‐Vinyl and Alkynyl Sulfones by the Formation of an Electron Donor‐Acceptor Complex Using Thiosulfonates and Sodium Iodide Under Visible Light

“…On the basis of control experiments and previous works, [38,50,51,60,64,[66][67][68] one possible reaction mechanism was proposed as shown in Scheme 4. Compound 2 a and NaI form an EDA complex, which then undergoes single electron transfer to form the sulfonyl radical B, the sulfur anion PhS À A and the iodine radical under light irradiation.…”

“…As a sulfur-containing reagent, thiosulfonate is characterized by being odorless and environmentally friendly, which has attracted the attention of many chemists. [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49] Therefore, a variety of methods for cracking thiosulfonates into active species have been developed as shown in Scheme 1a, (1), [35] (2), [38,50,51] (3), [31,50,52,53] (4), [32,36,37,40,[54][55][56][57] leading to various methods for construction of CÀ S bonds. Despite the significance of these approaches, there are still plagued by at least one of the following limitations: (1) the use of transition metal catalysts, (2) the need for high reaction temperature, (3) the necessity of photocatalysts and, (4) hyperoxides as oxidants.…”

Copper-Catalyzed Trifluoromethylthio-arylsulfonylation of Styrene Derivatives via the Insertion of Sulfur Dioxide

“…In a pioneering study, Xu and co-workers utilized a dual gold/photoredox catalysis strategy in which compounds containing both the SCF 3 group and sulfonyl skeleton could be effectively produced (Figure a) . Although this protocol represents a breakthrough in thio-sulfonylation reactions of olefins, the requirement for two precious metal salts (Au and Ru) and the demand for poorly accessible aryl sulfonothioate (ArSO 2 SCF 3 ) have largely restricted its applications.…”