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.

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,...

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.

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.

The sulfur oxygen (S…O) interaction was used herein to obtain the (Z)-selective anti-Markovnikov vinyl sulfides from the addition of thiyl radicals to terminal alkynes. DFT calculations predicted that S···O interaction...