Organic Hydrogen Phosphite Or Hydrogen Phosphate Catalyed Friedel Crafts Amidoalkylation Reaction And Dinuclear Catalysts Applications In Asymmetric Reactions

1. Organic Hydrogen Phosphite or Hydrogen Phosphate CatalyzedFriedel-Crafts Amidoalkylation of Indoles with N-Ts Aryl Aldimines A highly efficient and selective Friedel-Crafts amidoalkylation reaction of indoles with N-Ts aryl aldimines has been developed utilizing dimethyl hydrogen phosphite or diphenyl hydrogen phosphate as the organocatalyst, providing a facile and efficient processes for synthesis of mono(indolyl)methanamine derivatives in good to excellent yields. This transformation displays a broad substrate scope and wide functional-group tolerability, regardless of the electronic and steric properties of N-Ts aryl aldimines. Given that the developed catalytic Friedel-Crafts amidoalkylation reaction exhibits several salient features such as metal-free catalysis, high efficiency, low cost and mild reaction condition, this process might has practical applications in the synthesis of 3-indolyl methanamine derivatives.2. Dinuclear Zinc Catalyzed Asymmetric Friedel-Crafts Amidoalkylation of Indoles with Aryl AldiminesThe asymmetric Friedel-Crafts amidoalkylation of indoles with aryl aldimines has been efficiently catalyzed by Trost's bis-ProPhenol dinuclear zinc complexes to attain 3-indolyl methanamine derivatives in good to excellent yields (85-98%) with moderate to high enantiomeric ratios (from 70:30 up to 95:5 er). Remarkablely, this approach provides efficient access to enantiomerically enriched 3-indolyl methanamines, which avoids the formation of the undesirable bis- and tris(indolyl)methanes (BIMs and TIMs) byproduct. 3. Asymmetric Epoxidation ofα,β-unsaturated ketones catalized by Chiral Dinuclear ZincTrost's dinuclear zinc catalysts are firstly applied into asymmetric epoxidation reaction ofα,β-unsaturated ketones. We find that the structures of ligands greatly influence on the catalytic behavior. With the optimized reaction conditions, the epoxidation reaction ofαβ-unsaturated ketones proceeds smoothly in the presence of tert-butyl hydroperoxide as the oxidants, which provide the desired epoxides in 89% yield and 83:17 er.