Copper-mediated stereospecific C–H oxidative sulfenylation of terminal alkenes with disulfides

Abstract

A copper and iodine-mediated C-H oxidative sulfenylation of olefins with diaryl disulfides has been developed for the stereospecific synthesis of vinyl thioether. With the combination of Cu(OTf)2 and I2, a variety of terminal alkenes underwent oxidative coupling reaction with various diaryl disulfides successfully to afford the corresponding E-vinyl sulfides in moderate to good yields.

Copper‐Promoted Thiolation of C(sp2)–H Bonds Using a 2‐Amino Alkylbenzimidazole Directing Group

“…or vinyl sulfone (7b, 80 %, 50°C) derivatives by treatment with H 2 O 2 in AcOH. [16] Since both the vinyl sulfinyl and vinyl sulfone derivatives are considered to be important building blocks in synthetic chemistry, [17] these transformations further demonstrate the possible application of our approach. The MBIP group could be smoothly removed and recovered through an N-Boc protection (Boc = tert-butoxycarbonyl) and hydrazinolysis sequence (Scheme 3).…”

Access to Sulfides through Free Radical Reaction of Vinyl Halides with Thiols

“…of AIBN at 90°C for 6 h in toluene (Entry 15). Using less 2 a or conducting the reaction in benzene, chloroform or tetrahydrofuran decreased the isolated yield of 4 a (Entries 13,14,(16)(17)(18). Therefore, vinyl sulfide could be prepared using thiol from the corresponding vinyl iodide in reflux MeOH, or from the vinyl bromide or chloride in toluene at 90°C.…”

“…Vinyl iodide 1 d (115 mg, 0.5 mmol) and 2 a (66 mg, 0.6 mmol) gave 3 b as colorless oil (86 mg, 81%). 1 (11), 103 (7), 91 (16), 77 (18). The stereochemistry of 3 b was determined by coupling constants of hydrogens in double bond.…”

“…[11] Sulfide derivatives are also widely used as organic materials in polymer [12] and molecular electronics. [13] For the synthesis of vinyl sulfides, vinyl halides, [14] alkynes, [15] olefines, [16] thioketal, [7] sulfoxides, [17] or epoxides [18] are typically used as substrates reacting with various thiols or their derivatives [19] . For vinyl halide substrates, the synthesis of vinyl sulfides was initially conducted by cross-coupling reactions with lithium, sodium thiolate or indium trithiolate catalyzed by transition metal catalysts (Pd [14a-d] or Ni [14e,f] ).…”

Copper Catalyzed Iodosulfenylation of Styrenes by Dual C—H Oxidative Functionalization

“…The radical oxidative coupling of alkenes with disulfides could also directly provide vinyl sulfides, although harsh reaction conditions are commonly required. [6] In 2015, our group [7] reported copper-mediated C-H oxidative sulfenylation of terminal alkenes with disulfides for the stereospecific synthesis of vinyl thioethers (Scheme 1). In past decades, the bifunctionalization of olefins has gained more and more attention in organic synthesis.…”