A novel copper-catalyzed one-pot trifluoromethylation/aryl migration/desulfonylation and C(sp(2))-N bond formation with conjugated tosyl amides as starting materials is presented here. The reaction affords α-aryl-β-trifluoromethyl amides bearing a quaternary stereocenter or trifluoromethylated oxindoles in a regioselective manner.

Metal-free: The first metal-free aryltrifluoromethylation of activated alkenes has been developed. With this method, trifluoromethylated isoquinolinediones, spirobicycles, oxindoles, and α-aryl-β-trifluoromethylamides were obtained with high control of the regioselectivity.

2D (1)H,(89)Y heteronuclear shift correlation through scalar coupling has been applied to the chemical-shift determination of a set of yttrium complexes with various nuclearities. This method allowed the determination of (89)Y NMR data in a short period of time. Multinuclear NMR spectroscopy as function of temperature, PGSE NMR-diffusion experiments, heteronuclear NOE measurements, and X-ray crystallography were applied to determine the structures of [Y(5)(OH)(5)(L-Val)(4)(Ph(2)acac)(6)] (1) (Ph(2)acac=dibenzoylmethanide, L-Val=L-valine), [Y(2)(OTf)(3)] (3), and [Y(2)(4)(OTf)(5)] (5) (2: [(S)P{N(Me)N=C(H)Py}(3)], 4: [B{N(Me)N=C(H)Py}(4)](-)) in solution and in the solid state. The structures found in the solid state are retained in solution, where averaged structures were observed. NMR diffusion measurements helped us to understand the nuclearity of compounds 3 and 5 in solution. (1)H,(19)F HOESY and (19)F,(19)F EXSY data revealed that the anions are specifically located in particular regions of space, which nicely correlated with the geometries found in the X-ray structures.

No abstract