Oxygen Dependent Switchable Selectivity during Ruthenium Catalyzed Selective Synthesis of C3-Alkylated Indoles and Bis(indolyl)methanes

Herein, we report a ligand-centered redox-controlled oxygen-dependent switchable selectivity during ruthenium-catalyzed selective synthesis of C3-alkylated indoles and bis­(indolyl)­methanes (BIMs). A wide variety of C3-alkylated indoles and BIMs were prepared selectively in moderate to good isolated yields by coupling a wide variety of indoles and alcohols, catalyzed by a well-defined, air-stable, and easy-to-prepare Ru­(II)-catalyst (1a) bearing a redox-active tridentate pincer (L 1a ). Catalyst 1a efficiently catalyzed the C3-alkylation of indoles under an argon atmosphere while, under an oxygen environment, exclusively producing the BIMs. A few drug molecules containing BIMs were also synthesized efficiently. 1a exhibited excellent chemoselectivity with alcohols containing internal carbon–carbon double bonds. Mechanistic investigation revealed that the coordinated azo-aromatic ligand actively participates during the catalysis. During the dehydrogenation of alcohols, the azo-moiety of the ligand stores the hydrogen removed from the alcohols and subsequently transfers the hydrogen to the alkylideneindolenine intermediate, forming the C3-alkylated indoles. While under an oxygen environment, the transfer of hydrogen from the ligand scaffold to the molecular oxygen generates H2O2, leaving no scope for hydrogenation of the alkylideneindolenine intermediate, rather than it undergoing 1,4-Michael-type addition forming the BIMs.