A Rh(Ⅱ）-catalyzed Multi-component Reaction Of Triazoles, Indole With Paraformaldehyde And Asymmetric Study Of Capturing Ammonium Ylide By Aromatic Aldehyde

Multi-component reactions have attracted numerous attention in modern organic synthesis because of their high efficiency, high atom economy and easy operation, and they play important role in building many complex polyfunctional compounds. In recent years, our group has been dedicated to study a series of multi-component reactions which based on capturing active ylides intermediates. To our delight, the reactions have achieved high yield, high diastereoselectivity and enantioselectivity, and successfully synthetized many structurally diverse compounds. However, the scope of substrate and catalysis of reactions are still to be expanded.In second chapter, we firstly combined the Rh(I) catalyst with hayashi ligand to cooperatively catalyze the ylide-participated three-component reactions, and we successfully achieved the asymmetric study of Aldol addition reaction that the aromatic aldehyde compounds captured the active ammonium ylide and successfully expanded the phenyl diazo to alkyl diazo compound. The reactions achieved high yield, high stereoselectivity. Furthermore, we explained properly the mechanism of reaction. However, the application and improvement of these catalysts in multi-component reactions require further research and exploration.In third chapter, we aimed at the multi-component reactions involving N-sulfonyltriazoles compounds. We first studied the a-imino metal carbenoid derived from N-sulfonyltriazoles, and tried to use electrophiles to trap the zwitterionic intermediates produced by N-sulfonyltriazoles and C(2)-substituted indoles. To our surprise, when we characterized the product by single-crystal X-ray analysis, we found the reaction didn’t accord with our designed pathway, it’s more interesting that the substrate may take place intermolecular recombination and produced amusing product a-amino-β-indole ketones.The mechanism of this new reaction were explored by the control experiments and the theoretical calculation investigation.In summary we successfully combined the Rh(I) catalyst with hayashi ligand to cooperatively catalyze the alkyl diazo compound-participated multi-component reaction for the first time. Secondly, we have developed a novel N-sulfonyltriazoles-participated multi-component reactions and the established method provides an high effient approach to synthetize a-amino-β-indole ketones。...