Abstract
Noncovalent sulfur···oxygen interactions can increase the stability of chalcogen ortho-substituted phenoxyl radicals. This effect contributes to transforming the 7-hydroxybenzo[b]thiophene moiety in a privileged structural motif to enhance the activity of phenolic antioxidants. A cascade of five consecutive electrophilic reactions occurring in one pot afforded potent and biocompatible α-tocopherol-like antioxidants.