(Z)-Selective anti-Markovnikov or Markovnikov thiol-yne-click reactions of an internal alkyne by amide hydrogen bond control

Herein, we show exclusive control of stereo and regioselective thiol-yne click (TYC) reactions of internal alkynes via amide hydrogen bond control. By exploiting appropriate hydrogen bonding interactions like N-HMIDLINE HORIZONTAL ELLIPSISS, N-HMIDLINE HORIZONTAL ELLIPSISN and C-HMIDLINE HORIZONTAL ELLIPSISO, either (Z)-selective anti-Markovnikov or Markovnikov products could be obtained for an internal alkyne, exclusively.