Iron-Catalyzed\nDirected C(sp²)–H\nand C(sp³)–H Functionalization with Trimethylaluminum

Abstract

Conversion of a C­(sp²)–H or C­(sp³)–H\nbond to the corresponding C–Me bond can be achieved by using\nAlMe₃ or its air-stable diamine complex in the presence\nof catalytic amounts of an inorganic iron­(III) salt and a diphosphine\nalong with 2,3-dichlorobutane as a stoichiometric oxidant. The reaction\nis applicable to a variety of amide substrates bearing a picolinoyl\nor 8-aminoquinolyl directing group, enabling methylation of a variety\nof (hetero)­aryl, alkenyl, and alkyl amides. The use of the mild aluminum\nreagent prevents undesired reduction of iron and allows the reaction\nto proceed with catalyst turnover numbers as high as 6500.