Brønsted acid-catalyzed solvent-controlled regioselective hydrothiolation and diastereoselective cascade cyclization of dienes.

A highly regio- and diastereo-selective Brønsted acid-catalyzed tandem hydrothiolation/Friedel-Crafts reaction of linear 1,3-dienes has been developed for the first time, which provides a metal-free and atom-economic way of constructing thiochromane derivatives. Meanwhile, by changing the solvent, 4,3-addition hydrothiolation of 1,3-dienes was also discovered. The origin of the observed selectivity was explained by density functional theory calculations.