Dehydroxylated C-3 Alkylation of Indole Accompanied by 1,2-Sulfur Migration

A metal-free sulfur neighboring group participation C-3 alkylation method between β-sulfur-α-alcohol and indole is documented. Due to its considerable generality and excellent selectivity, this method has been provided a facile access to synthetically useful α-indole-β-functions. Meanwhile, unlike traditional Friedel–Crafts and Mitsunobu reactions, the unique chemoselectivity and regioselectivity may be attributed to a synergetic mechanism with simultaneous C–O cleavage, C–S migration, and C–C formation occurring in the developed reaction.