The Research Of New Double Axially Chiral Bisphosphorylimide Catalyzed Asymmetric Self-coupling Reaction Of Enamides And Asymmetric Friedel-crafts Alkylation Of Indole

A structural unit containing a chiral carbon atom is present in a wide variety ofcompounds, particularly in the compounds of the life-related substances, such asproteins, lactic acid, glucose and nucleic acid and so on, which all contain chiralcarbon atoms. Constructing the chiral carbon atom structure unit by the method ofasymmetric catalytic has always been a hotspot in research of organic chemistry. Inthis paper, we investigated the asymmetric self-coupling reaction and asymmetricFriedel-Crafts reaction using the new double axially chiral bisphosphorylimideBr nsted acid catalyst. good catalytic results have been achieved, specificexperimental contents and results are as follows:Firstly, we introduced the significances and difficulties of building the chiralcarbon atom structure unit. through the development in the field of asymmetriccatalytic in the last two decades, we introduced the application of the metal catalystsystem and organocatalyst in constructing the chiral carbon atom structure unit andhighlighted the construction of chiral quaternary carbon center through the directlynucleophilic addition reactions of ketones and ketimines.Secondly, seven new double axially chiral bisphosphorylimide catalysts designedand synthesized by our group were applied to catalyze asymmetric self-coupling reaction of α-aryl enamides. We screened a series of reaction conditions, which mayinfluence the yield and stereoselectivities of this reaction. Such as catalyst, reactionsolvents, reaction temperature, reaction time and dosages of molecular sieve. Underthe optimal condition(-10℃, the tetrachloromethane as solvent,1equivalentenamides and5mol%3,3’ position of2naphthyl-(R)-H8-BINOL bisphosphorylimidederivatives as catalyst,15mg5molecular sieve as additive). We investigated10kinds of α-aryl enamides and obtained excellent results. the products of asymmetricself-coupling of enamides reaction were obtained in high enantioselectivities (up to98%ee) and high yields (up to94%). The1H NMR,13C NMR and HPLC of thereaction products were all characterized.Thirdly, nine new double axially chiral bisphosphorylimide catalysts designedand synthesized by our group were applied to catalyze asymmetric Friedel–Craftsalkylation of indole with3-hydroxyisoindolin-1-one, we screened a series of reactionconditions, which may influence the yield and stereoselectivities of this reaction. Suchas catalyst, reaction solvents, reaction temperature, reaction time, the kinds anddosages of additives. Under the optimal condition, we obtained medium yield andenantioselectivity. This result did not achieve the goal we expected, the relate work isin further exploration.Overall, the eleven new double axially chiral bisphosphorylimide catalysts wereapplied to catalyze asymmetric self-coupling reaction of α-aryl enamides andasymmetric Friedel-Crafts reaction. Good catalytic results have been achieved. Weextended the reaction types by optimizing the structure of the catalysts and thereaction conditions and provided some new ideas for asymmetric organic synthesis.