Synthesis Of Selenides And Asymmetric Axial Chiral Compounds Via C-H/N-H Functionalization Strategy

This thesis mainly focuses on the synthesis of selenides and asymmetric axial chiral compounds based on the strategy of C-H or N-H functionalization.The first part is enantioselective atropisomeric anilides synthesis via Cu-catalyzed intramolecular adjacent C-N coupling;The second part is palladium/norbornene-catalyzed ortho-acylation and ipso selenation via C(O)-Se bond cleavage.Chapter 1:C-N axially chiral compounds are widely existed or applied in the fileds of medicine,pesticide,natural products and catalysis.However,catalytically asymmetric synthesis of C-N axially chiral compounds has been less documented,which is possibly attributed to the relatively lower atropo-stability of C-N bonds and the hard reactions conditions for the construction.We developed a catalytic system of copper and chiral ligands derived from cyclohexanediamine,and we succeeded in the synthesis of aryl lactams via enantioselective intramolecular Ullmann-type amination reaction.The C-N axial chirality was induced efficiently by the intramolecular C-N cross-coupling.Moreover,it has the advantages of mild reaction conditions,easy preparation of raw materials,wide scope of substrates,high yield(99%yield)and excellent enantioselectivity(99%ee).Chapter 2:Selenides,the major form of selenium existing in our body,perform irreplaceable functions in life,but it is always a difficult problem to synthesize complex aryl selenides by mild methods.We developed a palladium/norbornene catalyzed ortho-carbonylation or alkoxycarbonylation and ipso selenylation reaction via the cleavage of the C(O)-Se bond of selenoates.Some importat steps including the activation of C-H bond of aryl iodides and formation of the critical palladacycle intermediate are highlighted.Various of selenides with high yield could be obtained,the reaction has the advantages of mild reaction conditions and broad substrate scope.