Electrochemical radical-mediated selective C(sp 3 )-S bond activation.

Selective C(sp 3 )-S bond breaking and transformation remains a particularly important, yet challenging goal in synthetic chemistry. Over the past few decades, transition metal-catalyzed cross-coupling reactions through the cleavage of C(sp 3 )-S bonds provided a powerful platform for the construction of target molecules. In contrast, the selective activation of widespread C(sp 3 )-S bonds is rarely studied and remains underdeveloped, even under relatively harsh conditions. Herein, a radical-mediated electrochemical strategy capable of selectively activating C(sp 3 )-S bonds is disclosed, offering an unprecedented method for the synthesis of valuable disulfides from widespread thioethers. Importantly, compared with conventional transition-metal catalyzed C-S bond breaking protocols, this method features mild, catalyst- and oxidant-free reaction conditions, as well excellent chemoselectivity towards C(sp 3 )-S bonds. Preliminary mechanistic studies reveal that sulfur radical species are involved in the reaction pathway and play an essential role in controlling the site-selectivity.