Enantioselective Friedel−Crafts Alkylations Catalyzed by Bis(oxazolinyl)pyridine−Scandium(III) Triflate Complexes

The enantioselective Friedel−Crafts addition of a variety of indoles catalyzed by bis(oxazolinyl)pyridine−scandium(III) triflate complexes (Sc(III)−pybox) was accomplished utilizing a series of β-substituted
α,β-unsaturated phosphonates and α,β-unsaturated 2-acyl imidazoles. The acyl phosphonate products
were efficiently transformed into esters and amides, whereas the acyl imidazole adducts were converted
to a broader spectrum of functionalities such as esters, amides, carboxylic acids, ketones, and aldehydes.
The sense of stereoinduction and level of enantioselectivity were found to be functions of the size of the
substrate employed, the substitution on the ligand, and the catalyst loading. Molecular modeling of the
catalyst with the bound substrates was performed based on the crystal structures of the catalyst complexes
and the sense of stereoinduction observed in the addition reaction. Nonlinear effects over a range of catalyst
concentrations implicate a mononuclear complex as the active catalyst.