Markovnikov or anti-Markovnikov selective thiol-ene click (TEC) reactions and the synthesis of β-hydroxysulfides via aerial dioxygen activation are prevalent C-S bond forming reactions of styrenes and thiophenols. Herein, by choosing appropriate environments using solvents with additives or neat conditions, any one of these three reactions was achieved exclusively in excellent yields.

Hydrogen bonding interactions like N–H⋯S, N–H⋯N and C–H⋯O helped to obtain either (Z)-selective anti-Markovnikov or Markovnikov Thiol–Yne-Click products exclusively with excellent yields from an internal alkyne under metal free conditions.

Organosulfur compounds are omnipresent in many drugs, natural products, and functional materials; therefore, methodologies of C−S bond formation reactions are desirable in synthesis. The recent trend to control many chemical reactions by cooperative multiple weak interactions have emerged as one of the popular topics in supramolecular catalysis. Herein, we have made a collection of literature which utilizes multiple noncovalent interactions like H-bonding, solvent bonding, S−H•••π, C−H•••π, π−π stacking, charge-transfer complexation, etc. toward aryl C−S bondformation reactions.

In organic synthesis, transition metal and photoredox catalysis based reaction systems are the emerging trends for construction of C-S bonds. Many review articles have timely appeared in this field, however,...

Herein we demonstrate that an anti-Markovnikov selective thiol-yne-click (TYC) reaction could be achieved between phenyl acetylenes and thiophenols by exploiting a newly identified SÀ H···π non-covalent interaction without using any catalysts, additives and solvents. Natural bond orbital (NBO) analyses also supported that SÀ H···π and cooperative π-π stacking interactions helped to promote this regioselective reaction. The hydrothiolated products were isolated in near quantitative yields. Also, the concept of selfsorting was demonstrated when styrene, phenyl acetylene and thiophenols were reacted in one pot. Owing to the stronger SÀ H···π preference of ethynyl � H over the vinyl = H hydrogen bond, selectively, TYC product formation was found to be dominating over the thiol-ene-click (TEC) product.

Due to the normal polarity preferences, arenes form stable complexes with thiols through SÀH···p interaction and direct dehydrogenative aryl CÀS coupling is usually restricted. We report here an umpolung based one pot and direct CÀS coupling approach under metal free and mild condition. Electrophile sulfenium ions were generated in situ from thiols using iodine(III) reagent PhI(OAc) 2 (PIDA) and subsequently used for aromatic electrophilic substitution (EArS) to synthesize diaryl sulfides. Also by using of appropriate amount of PIDA, cascaded synthesis of CÀS and S=O bonds led to aryl sulfinyl arenes in one pot. Covalent self-sorting or competitive experiments further confirmed the involvement of sulfenium ion in the EArS.

An iodine-triggered dioxygen activation in oxysulfonylation reactions of unactivated olefins using sulfonyl hydrazides and iodine as catalyst is reported here.I no ne pot,n earq uantitative syntheses of b-hydroxysulfones were achieved at 70 8 8C, within 7h,i na cetonitrile and under aerobic conditions.A plausible mechanism is established by radical trapping and 18 Ol abellinge xperiments for the operation-ally simple,e fficienta nd economically viable transformation. Thed irect activation of aerial oxygen under metal-free and mild conditions is proposed for the oxysulfonylation of olefins.

Herein we report the use of N-iodosuccinimide (NIS) as a bifunctional reagent for a regio-and (E)-selective C (sp 2 )-H sulfonylation reaction of styrenes. Styrenes and sulfonyl hydrazides treated with NIS and potassium carbonate in ethanol at 70°C resulted in (E)-vinyl sulfones exclusively with good to excellent yields. NIS, plays a dual role to generate sulfonyl radical from sulfonyl hydrazides at an initial stage and finally gives β-iodosulfone intermediate which was further converted to (E)-vinyl sulfones. Overall, a sustainable method for mild, metal free, convenient, one pot and direct synthesis of (E)-vinyl sulfones from styrenes are demonstrated via a CÀ S coupling reaction. Scheme 1. The present work: a) Direct synthesis of (E)-vinyl sulfone from styrenes using N-iodosuccinimide as b) The small molecule system chemistry approach via bifunctionality of NIS. . (E)-1-Methyl-4-((4-(trifluoromethyl)styryl)sulfonyl)benzene (3 ja): [22b] R f = 0.4 (20% ethyl acetate in hexane); white solid; yield 96% (128 mg); mp 120-124°C (lit. [22b] 120-122°C); 1 H NMR (400 MHz, CDCl 3 ) δ 7.83 (d, J = 8.2 Hz, 2H),7.67 (d, J = 15.4 Hz, 1H), 7.64 (d, J = 8.2 Hz, 2H), 7.58 (d, J = 8.2 Hz, 2H), 7.36 (d, J = 8.2 Hz, 2H), 6.94 (d, J = 15.4 Hz, 1H), 2.44 (s, 3H); 13 C NMR (175 MHz, CDCl 3 ) δ 145.0, 140.0, 137.3, 136.0, 132.7 (q, 2 (E)-4-(2-Tosylvinyl)benzonitrile (3 ka): [22b] R f = 0.4 (20% ethyl acetate in hexane); white solid; yield 91% (120 mg); mp 125-128°C (lit. [22b] 125-127°C); 1 H NMR (400 MHz, CDCl 3 ) δ 7.83 (d, J = 8.2 Hz, 2H), 7.68 (d, J = 8.4 Hz, 2H), 7.64 (d, J = 15.4 Hz, 1H), 7.56 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 8.2 Hz, 2H), 6.95 (d, J = 15.4 Hz, 1H), 2.45 (s, (E)-1-Methyl-4-((4-nitrostyryl)sulfonyl)benzene (3 la): [28c] R f = 0.45 (20% ethyl acetate in hexane); white solid; yield 84% (103 mg); mp 172-174°C (lit. [28c] 172-175°C); 1 H NMR (700 MHz, CDCl 3 ) δ 8.24 (d, J = 8.8 Hz, 2H), 7.84 (d, J = 8.2 Hz, 2H), 7.69 (d, J = 15.4 Hz, 1H), 7.63 (d, J = 8.8 Hz, 2H), 7.38 (d, J = 8.2 Hz, 2H), 6.99 (d, J = 15.4 Hz, 1H), 2.45 (s, 3H); 13 (E)-1-Methyl-4-((4-nitrostyryl)sulfonyl)benzene (3 la): [28c] R f = 0.45 (20% ethyl acetate in hexane); white solid; yield 84% (103 mg); mp 172-174°C (lit. [28c] 172-175°C); 1 H NMR (700 MHz, CDCl 3 ) δ 8.24 (d, J = 8.8 Hz, 2H), 7.84 (d, J = 8.2 Hz, 2H), 7.69 (d, J = 15.4 Hz, 1H), 7.63 (d, J = 8.8 Hz, 2H), 7.38 (d, J = 8.2 Hz, 2H), 6.99 (d, J = 15.4 Hz, 1H), 2.45 (s, 3H); 13