Br?nsted Acid Catalyzed Friedel-Crafts Alkylation Of Tertiary Arylamines And Amidation Of C(sp~3)-H

Br?nsted acid has been widely used as a powerful catalyst in multitudinous organic reactions.Currently,Br?nsted acid catalysts were widely used in organic reaction designing since the development of chiral Br?nsted acid catalyst and merging of different catalytic modes.In this dissertation,we applied Br?nsted acid as basis.Firstly,we used chiral Br?nsted acids as the single catalyst to develop Friedel-Crafts reaction of tertiary Arylamines.Then,we explored α-amidation of tertiary arylamines in dual catalytic modes,due to the potential of merging photoredox catalysis and Br?nsted acid catalysis.This paper is mainly divided into the following three parts.In the first part,we first introduced the development of Br?nsted acids and chiral phosphoric acid catalysts.Then we introduced two types of chiral phosphoric acid catalytic modes used in Friedel-Crafts reaction,depending on the different mechanisms.At last,recent research focus on synergetic strategy with combing photoredox catalysis and Br?nsted acid catalysis was illustrated and remaining problems were discussed.In the second part,due to the advantages of SPINOL chiral phosphoric acid catalysts,we first introduced the development of Friedel-Crafts reaction using chiral phosphoric acid catalysts,and we found Friedel-Crafts alkylation of tertiary arylamines is still challenging.Based on this information,we designed and developed enantioselective Friedel-Crafts alkylation of tertiary arylamines.We used imine and tertiary arylamines as substrates.It is a perfect encounter of chiral Br?nsted acid catalyst with basic substrate.Then we studied the further application of this reaction.In the third part,we first introduced several examples of imine ion generated by photoredox catalysis and the use of isocyanide in organic synthesis.Based on it,we designed a direct α-amidation of tertiary arylamines by merging photoredox catalysis and Br?nsted acid catalysis.And we successfully obtained a series of corresponding products in the mild reaction condition.