Ruthenium-Catalyzed <i>ortho</i>/<i>meta</i>-Selective Dual C–H Bonds Functionalizations of Arenes

The first example of transition-metal-catalyzed <i>ortho</i>/<i>meta</i>-selective dual C–H functionalizations of arenes in one reaction is described. In this transformation, <i>ortho</i>-C–H chlorination and <i>meta</i>-C–H sulfonation of 2-phenoxypyri­(mi)­dines were achieved simultaneously under catalysis by [Ru­(<i>p</i>-cymene)­Cl₂]₂. The other reactant, namely, an arylsulfonyl chloride, played the role of both a sulfonation and chlorination reagent. More importantly, the arylsulfonyl chloride was also an oxidant in the process. Mechanistic studies indicated that six-membered ruthenacycles were the key intermediate in the reaction