Straightforward and highly efficient catalyst-free regioselective reaction of thiol to β-nitrostyrene: a concise synthesis of vinyl sulfide and nitro sulfide

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

“…If radical initiator AIBN were used and with a solvent, the reactions gave vinyl sulfides 28 through a radical addition and nitro group elimination process (Scheme 17). 52 …”

Denitrative Cross-Couplings of Nitrostyrenes

“…Although each proposal differs in detail, the main three characteristic steps feature in all proposals. Firstly, carbon- or heteroatom-centered radical 4 is generated in situ by various methods from precursors 6 – 33 [ 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 ]. These include a thermal homolytic cleavage of labile bonds, metal-catalyzed and photochemically initiated processes.…”

“…The most explored is the formation of C-S and C-P bonds with the heteroatom at different oxidation states. The first example of denitrative cross-coupling leading to the formation of a new C-heteroatom bond was reported in 2009 ( Scheme 18 ) [ 38 ]. Yao investigated a reaction of nitrostyrenes 1 with thiols 22 , under various reaction conditions.…”

Microwave-promoted regio- and stereoselective vinylation of heterocyclic thiols

“…In a way similar to vinyl halides, b-nitrostyrene can also be coupled with thiols to afford vinyl suldes as mixture of E/Z compounds. 7 However, inert atmosphere and an initiator are required for improved yield of the products. On the other hand, hydrothiolation of terminal alkynes is the more common and pursued method for preparing vinyl suldes and as such there are numerous reports of this method under various conditions.…”

“…Most of the reported procedures on the hydrothiolation reaction of terminal alkynes to afford vinyl suldes have focused on various thiols like aromatic, alkyl and benzyl thiols. [5][6][7][8][9][10][11] Conversely, report's regarding the participation of heterocyclic thiols in hydrothiolation reaction of terminal alkynes is signicantly lagging behind. In this regard, we have recently developed an indium catalyzed hydrothiolation of terminal alkynes with heterocyclic thiols to obtain vinyl suldes 12 (path a, Scheme 1) via the more challenging Markovnikov mode of addition.…”