Asymmetric[3+2]/[8+4] Cycloaddition Catalyzed By Secondary Amine And Design And Synthesis Of Novel Spiropyrrolidine Secondary Amine Catalyst

Since the beginning of this century,secondary amine catalysis has experienced a rapid development stage,and has already played a pivotal role in the field of asymmetric catalysis,providing new ideas for the asymmetric synthesis of natural products and pharmaceutical molecules.This thesis is mainly devoted to the development of asymmetric reactions types in the dieneamine or tetraenamine catalysis mode and the design and synthesis of new spiropyrrolidine secondary amine catalysts.It mainly includes the following three aspects:1.Secondary Amine Catalyzed Asymmetric[3+2]Cycloaddition Reaction to Synthesize Cyclopenta[b]indole CompoundsThe asymmetric[3+2]cycloaddition reaction of α,β-unsaturated aldehyde with 2-indole methanol was achieved by the synergistic catalytic system of chiral secondary amine catalyst,palladium complex and Bronsted acid.It has afforded cyclopenta[b]indole derivatives containing two stereocenters in high yields(up to 99%)with excellent stereoselectivities(up to>20:1 dr,up to 99%ee).The present strategy is obviously complementary to previous methods for the synthesis of cyclopenta[b]indole with high efficiency.2.Design,Synthesis and Application of Novel Spiropyrrolidine Secondary Amine CatalystsBased on the research of Cu-catalyzed asymmertic asymmetric 1,3-dipolar cycloaddition in our laboratory,a new type of spiropyrrolidine secondary amine catalyst was designed and synthesized.And then applied to asymmetric cycloaddition reactions catalyzed by enamines,dienamines,and tetraenamines.Although it did not achieve excellent results,it had a guiding effect on the reformation of our later catalysts.3.Secondary Amine Catalyzed Asymmetric[8+4]Cycloaddition Reaction to Synthesize Bicyclo[4.2.1]nonane CompoundsAsymmetric[8+4]cycloaddition reaction of 2-indenaldehyde with pyrrole diene catalyzed by secondary amines was achieved.By screening the reaction conditions,a good yield(87%)and enantioselectivity(75%)were obtained.The universality of the reaction substrate was also explored,and good results were obtained.