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

Abstract

AbstractIr‐catalyzed transformations initiated by sulfur‐directed vinylic sp2 and benzylic sp3 C−H activation are disclosed that achieve the construction of sulfur‐containing seven‐ and eight‐membered systems. Allyl 2‐alkynylphenyl sulfides were transformed into dihydrobenzothiepines in 30–95 % 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.