Ruthenium-Catalyzed Monoalkenylation of Aromatic Ketones by Cleavage of Carbon-Heteroatom Bonds with Unconventional Chemoselectivity

Ruthenium-catalyzed selective monoalkenylation of ortho C-O or C-N bonds of aromatic ketones was achieved. The reaction allowed the direct comparison of the relative reactivities of the cleavage of different carbon-heteroatom bonds, thus suggesting an unconventional chemoselectivity, where smaller, more-electron-donating groups are more easily cleaved. Selective monofunctionalization of C-O bonds in the presence of ortho C-H bonds was also achieved. Smaller is better: The title reaction for ortho C-O and C-N bonds of aromatic ketones was achieved. Direct comparison of the cleavage of the carbon-heteroatom bonds suggested an unconventional chemoselectivity, where smaller, more-electron-donating groups are more easily cleaved. Selective monofunctionalization of C-O bonds in the presence of ortho C-H bonds was also achieved.