Sulfide‐Directed Ir‐Catalyzed Vinylic sp2 and Benzylic sp3 C–H Activation for the Construction of Sulfur‐Containing Medium‐Ring System

We here disclose Ir-catalyzed transformations initiated by sulfur-directed vinylic sp2 and benzylic sp3 C–H activation, and achieved the construction of sulfur-containing seven- and eight-membered systems. Allyl 2-alkynylphenyl sulfides were transformed into dihydrobenzothiepines in 30-90% yield, and 2-alkynylaryl 2-tolyl sulfides were converted into dibenzo[b,f]thiepines in 57-95% yield along with double bond isomerization. In both reactions, the combination of Ir catalyst and sulfide moiety was a key to the facile cyclization.