Electrophilic phosphonium cations catalyze hydroarylation and hydrothiolation of olefins.

Electrophilic phosphonium cations (EPCs) are efficient main group catalysts for the hydroarylation of olefins under mild conditions, providing a facile route to substituted aniline, bis-arylamine, phenol, furan, thiophene, pyrrole, and indole derivatives. Similarly, EPCs catalyze the hydrothiolation of aryl olefins with thiophenol affording a series of alkyl aryl thioethers. Experimental data support a mechanism for these reactions that involves initial activation of the olefin.