Nickel-Catalyzed, para-Selective, Radical-Based Alkylation of Aromatic Ketones.

A direct, para-selective, radical-based alkylation of aromatic ketones with alkanes has been developed using a nickel catalyst with oxamide as the ligand. Acetophenones bearing electron-withdrawing substituents were functionalized directly with simple alkanes with high para-selectivity while acetophenones with electron-donating groups were mainly para-functionalized. A mechanistic study indicated that C-H bond activation of the aromatic ring may be the rate-determining step of the reaction.

Mn-Enabled Radical-Based Alkyl-Alkyl Cross-Coupling Reaction from 4-Alkyl-1,4-dihydropyridines.

Highly efficient alkylation of ß-chloro ketones and their derivatives was achieved by means of domino dehydrochlorination/Mn-enabled radical-based alkyl-alkyl cross-coupling reaction. In situ-generated α,ß-unsaturated ketones and their analogues were identified as the reaction intermediates. Known bioactive compounds, such as melperone and azaperone, could be easily prepared from ß-chloropropiophenone in two steps.