Base-Promoted, Aerobic, and Regioselective Carbon–Hydrogen Bond Activation of Thiophene with Group 9 Metalloporphyrins

Base-promoted aerobic carbon–hydrogen bond activation (CHA) of thiophene was achieved with high regioselectivity at the 2-position by group 9 metalloporphyrins in moderate to high yields. Mechanistic investigations suggest a homolytic aromatic substitution through M^II(ttp) (M = Rh, Ir) metalloradical addition, followed by β-elimination of a metal hydride pathway

Facile Aerobic Alkylation of Rhodium Porphyrins with Alkyl Halides

Alkylation of rhodium porphyrins was achieved in moderate to high yields in the presence of air and water. With this facile alkylation method, various alkyl Rh^III(por) species, including those with tertiary alkyl, were synthesized. Mechanistic investigations suggest a parallel S_N2 via [Rh^I(ttp)]⁻ with halogen atom transfer pathway via [Rh^II(ttp)]^•