Catalytic Enantioselective Amination of Enol Silyl Ethers Using a Chiral Paddle-Wheel Diruthenium Complex.

A chiral paddle-wheel dinuclear ruthenium catalyst was applied to a catalytic asymmetric nitrene-transfer reaction with enol silyl ethers. The ruthenium catalyst was applicable to aliphatic enol silyl ethers as well as aryl-containing enol silyl ethers. The substrate scope of the ruthenium catalyst was superior to that of analogous chiral paddle-wheel rhodium catalysts. α-Amino ketones derived from aliphatic substrates were obtained in up to 97% ee with the ruthenium catalyst, while analogous rhodium catalysts resulted in only moderate enantioselectivity.

C-H γ,γ,γ-Trifluoroalkylation of Quinolines via Visible-Light-Induced Sequential Radical Additions.

The photocatalyst-free C-H γ,γ,γ-trifluoroalkylation of quinolines under visible light irradiation is reported. By the combination of readily available alkenes and Umemoto's reagent II, a variety of γ,γ,γ-trifluoroalkyl groups were installed into quinolines via chemoselective sequential radical processes. This transformation provides rapid access to a variety of quinoline derivatives with scarcely explored fluoroalkyl groups, affording a novel library of N-heteroaromatic compounds and versatile building blocks for applications in medicinal chemistry.