The Synthesis Of A Novel Chiral Camphor Schiff Base And Its Catalytic Asymmetric Friedel-Crafts Reaction

Chirality is universally present in natural world,which is normal attribute of natural.With the wide application of chiral compounds in medical drugs,biology and organic chemical reactions,the comprehension of chiral compounds are also got broadening and deepening.Among all the method of getting chiral compounds,asymmetric catalytic reactions are one of most important methods for getting chiral drug intermediates,such as asymmetric Henry reaction,asymmetric Aldol reaction,asymmetric Strecker reaction,asymmetric Friedel-Crafts reaction and so on.Therefore,study various asymmetric catalytic reactions,which give high catalytic efficiency with environmental friendly properties and can get wide application,is extremely important topics.The asymmetric Friedel-Crafts reaction is a general and wide applicative method for constructing C-C bonds,which has drawn extensive attention of synthesis chemists for long time.In the asymmetric catalytic reaction process,catalyst is a core research point.Promotion of the catalytic activity and selectivity should be started from developing new chiral catalyst.Camphor is one of cheap and readily available natural chiral materials,which has unique spatial stereostructure.But,a few modification positions in camphor molecule were stronger limited it's application in asymmetrical reaction.Our group devoted to study the synthesis and application of new chiral camphor derivatives.Some of important results already published.This thesis was focused on synthesis of the chiral camphor Schiff base and studies utility of its metal complexes in asymmetric reaction.This thesis is includes the following three parts:1.Literature review section.This part summarizes main research progresses on asymmetric Friedel-Crafts reactions and the application of camphor derivatives in asymmetric organic catalysis.2.Synthesis of chiral camphor Schiff bases and camphor amino alcohols.Chiral camphorsulfonic acid and natural chiral camphor were used as starting material to prepare 1,2-substituted camphor amino alcohols and 2,3-substituted camphor amino alcohols.Twelve kinds of chiral camphor Schiff bases were prepared by further reaction.The final products were characterized by nuclear magnetic resonance spectroscopy and high resolution mass spectrometry.3.Study of Asymmetric Friedel-Crafts alkylation of Pyrrole with ?,y-unsaturated-a-ketoesters.Twelve chiral camphor Schiff bases metal complexes were used to catalyze asymmetric Friedel-Crafts alkylation reaction of pyrrole and ?,y-unsaturated-a-ketoesters.Based on the results of experiments,L3 were selected as the optimal ligand,CuBr2 as a metal salt,toluene as a solvent,piperidine as the added alkaline,reaction at 5?.Under the optimized reaction conditions,this reaction shows the best chemical yields and enantioselectivity.This process also has good group tolerant,?,?-unsaturated-a-ketoesters with different substituents also can use as substrate to give good chemical yield and enantioselectivity.