Manganese(III)/Lewis Acid–Catalyzed Synthesis of <i>β</i> ‐Hydroxysulfones

An efficient method is developed for the synthesis of β ‐hydroxysulfones from difunctionalized olefins and substituted sodium sulfinates with Mn(OAc) 3 /Lewis acid catalyst through aerobic oxidation, which provides β ‐hydroxysulfones in middle to high yields with broad compatibility of functional groups. The high efficiency is attributed to the interaction between the Mn(III) species and Lewis acid such as Ce(OTf) 3 that enhances its redox potential, thus accelerating Mn(III)‐catalyzed sulfonyl radical formation from sulfonates through single‐electron transfer mechanism.