Efficient trans-hydroarylation of alkynes by simple arenes has been realized regio- and stereoselectively at room temperature in the presence of Pd(II) or Pt(II) catalysts and a mixed solvent containing
trifluoroacetic acid (TFA). Various arenes undergo trans-hydroarylation selectively across terminal and internal
C−C triple bondsincluding those conjugated to CHO, COMe, CO2H, and CO2Et groups, affording kinetically
controlled cis-arylalkenes predominantly in most cases, especially, in good yields for electron-rich arenes and
activated alkynes. The formation of arene/alkyne 1/2 or 2/1 adducts as side products is dependent on the
arenes' and alkynes' substituents, which can be suppressed in some cases by changing the catalyst, catalyst
concentration, and reaction time. The Pt(II) system, PtCl2/2AgOAc/TFA, shows lower catalytic activity than
Pd(OAc)2/TFA, but higher selectivity, giving higher yields of adducts at the same conversion. On the basis of
several isotope experiments and control reactions, a possible mechanism involving electrophilic metalation of
aromatic C−H bonds by in-situ-generated cationic Pd(II) and Pt(II) species leading to intermolecular trans-arylpalladation to alkynes has been discussed.