NMR Spectrocopic Characterization and DFT Calculations of Zirconium(IV)-3,3 -Br-2-BINOLate and Related Complexes Used in an Enantioselective Friedel Crafts Alkylation of Indoles with alpha, beta-Unsaturated Ketones

Experimental and theoretical studies on the structure of several complexes based on (R)-3,3'-Br-2-BINOL ligand and group (IV) metals used as catalysts in an enantioselective Friedel-Crafts alkylation of indoles with alpha,beta-unsaturated ketones have been carried out. NMR spectroscopic studies of these catalysts have been performed, which suggested that at room temperature the catalysts would form a monomeric structure in the case of Ti-IV and a dimeric structure in the cases of Zr-IV and Hf-IV. Density functional theory (DFT) calculations clearly corroborate the conclusions of these experimental spectroscopic studies. The dimeric structure with a doubly bridged motif [Zr-2(IV)(mu-(R)-3,3'-Br-2-BINOL)(2)] where each binaphthol ligand acts as bridge between the metal centers (Novak's model) is more stable than the dimeric structure with a doubly bridged motif [Zr-2(IV)(mu-(OBu)-Bu-t)(2)] where the tert-butoxide groups act as bridging ligands (Kobayashi's model). The scope of the Friedel-Crafts alkylation with regard to the indole structure has been studied. Finally a plausible mechanism for the Friedel-Crafts reaction and a stereomodel for the mode of action of the catalyst that explain the observed stereochemistry of the reaction products have been proposed.