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S−H⋅⋅⋅π Driven Anti‐Markovnikov Thiol‐Yne Click Reaction
Author(s) -
Choudhuri Khokan,
Pramanik Milan,
Mandal Arkalekha,
Mal Prasenjit
Publication year - 2018
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201800381
Subject(s) - chemistry , markovnikov's rule , click chemistry , regioselectivity , thiol , natural bond orbital , hydrogen bond , catalysis , sulfur , covalent bond , combinatorial chemistry , photochemistry , organic chemistry , medicinal chemistry , molecule
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 S−H⋅⋅⋅π non‐covalent interaction without using any catalysts, additives and solvents. Natural bond orbital (NBO) analyses also supported that S−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 self‐sorting was demonstrated when styrene, phenyl acetylene and thiophenols were reacted in one pot. Owing to the stronger S−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.