Photo-Induced<i>ortho</i>-C–H Borylation of Arenes through In Situ Generation of Rhodium(II) Ate Complexes
Jin Tanaka, Yuki Nagashima, Antônio Junio Araujo Dias, Ken Tanaka
Abstract
Photoinduced in situ “oxidation” of half-sandwich metal complexes to “high-valent” cationic metal complexes has been used to accelerate catalytic reactions. Here, we report the unprecedented photoinduced in situ “reduction” of half-sandwich metal [Rh(III)] complexes to “low-valent” anionic metal [Rh(II)] ate complexes, which facilitate ligand exchange with electron-deficient elements (diboron). This strategy was realized by using a functionalized cyclopentadienyl (CpA3) Rh(III) catalyst we developed, which enabled the basic group-directed room temperature ortho-C–H borylation of arenes.
Topics & Concepts
ChemistryBorylationRhodiumCyclopentadienyl complexCationic polymerizationCatalysisLigand (biochemistry)MetalPhotochemistryMedicinal chemistryIn situPolymer chemistryOrganic chemistryArylReceptorBiochemistryAlkylCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsCatalytic Cross-Coupling Reactions