Ring Nitrogen Sulfonylimine Aza-Henry Reaction And Asymmetry Of [3+2] Cycloaddition Preliminary Inquiry

The nucleophilic addition of imine is an important method for gaining amine, especially the additionof the cyclic imine is a direct and effective method for gaining nitrogen-containing heterocyclic compounds.In this paper, the Aza-Henry reaction of the N-sulfonyl cyclic imines is studied in aqueous phase. Inaddition, an asymmetric [3+2] cycloaddition of these cyclic imines catalyzed by bifunctional phosphine ispreliminarily explored.1. The Aza-Henry reaction of N-sulfonyl cyclic imines in water catalyzed by sodium carbonate isstudied.In chapter3, we discuss a series of Aza-Henry reactions in which we used benzosulfonyl cyclicimideand nitromethane as starting materials in aqueous phase (pure water). We concluded that the correspondingregular pattern by studying various influence factors of the reaction. Sodium carbonate, which was alow-cost and environmentally friendly inorganic base, is found to be an excellent catalyst for theAza-Henry reaction of N-sulfonyl cyclic imines under the mild conditions at18oC. The advantages of thismethod are wide substrates scope, mild conditions, and simple handing. Pure monosubstituted productswere obtained by recrystallization in petroleum ether and ethyl acetate with the yield over90%.Unfortunately, under this condition, the corresponding products of disubstituted benzene were not obtaineddue to the large steric benzosulfonyl cyclicimine. However, the corresponding products of disubstitutedbenzene were obtained by increasing the quantity of catalyst, increasing the temperature of reaction,prolonging the reaction time with the yield about80%. This method not only has practical application inthe preparation of β-nitro amines, but also has fully shown the application prospect in green chemistry.2. The preliminary results of asymmetric [3+2] cycloaddition for N-sulfonyl cyclic imines catalyzedby the bifunctional tertiary phosphine derived from proline is reported.In chapter4, we designed and synthesized bifunctional chiral tertiary phosphine catalysts with twochiral centers from D-proline, and investigated the catalytic behavior of the catalysts in a cyclic nitrogensulfonylimine and2,3-butadiene acid benzyl ester asymmetric [3+2] cycloaddition reaction. Thepreliminary study showed that the chiral tertiary phosphine catalysts can successfully catalyze the cycloaddition reaction of the ring nitrogen sulfonylimine and2,3-butadiene acid benzyl ester asymmetric[3+2], with moderate yield (75%yield) and low enantioselectivity (23%ee) were obtained. Furtherexploration of this catalytic system is under doing in our lab.