Synthesis Of 1,3-indandione Derivatives Via Chiral N-Heterocyclic Carbcne And Synthesis And Application Of Novel Chiral Bronsted Acid Catalysts

Since the beginning of this century,asymmetric organo-catalysis has become one of the hot research fields in asymmetric catalysis.The chiral organo-catalysis has the advantages of high stability,highly catalytic activity,good atomic economy and easy operation.Organo-catalyzed asymmetric reaction has become an efficient approach for the synthesis of abundant enantiomerically pure molecules with biological and pharmaceutical activities.Among all types of organic catalysts,the catalysts of chiral N-heterocyclic carbene(NHC)and Br(?)nsted acid have attracted much attention on account of their excellent catalytic efficiency.In this thesis,based on asymmetric desymmetrization strategy via chiral N-heterocyclic carbene catalysis,a series of optically active 2,2-disubstituted 1,3-indanedione compounds containing a chiral quaternary carbon center were constructed.According to literatures reported,those structures were endowed with potential biological and pharmaceutical activities Furthermore,we have synthesized a new type of optically pure binaphthyl(tert-butylsulfinyl)phosphoramidate catalyst with both axial and central chiralities The asymmetric Friedel-Crafts reaction between indoles and imines was preliminarily studied with this type of catalyst.In details,the research content includes two parts as follows.In the first part of the thesis,the asymmetric desymmetrization[4+2]cycloaddition reaction of cyclopentenediones with ?-methyl ?,?-unsaturated aldehydes was initiated,followed by methylation reaction.The reaction provided a method to build a series of optically active 2,2-disubstituted 1,3-indanedione derivatives in goods yield with high enantiomeric excesses via a chiral N-heterocyclic carbene catalyst derived from aminoindanol skeleton.This asymmetric process involves in cascade desymmetrizing Michael addition,aldol annulation and aromatization steps.Notably,the challenging remote chirality control of cyclopentenediones with an all-carbon quaternary stereogenic center was also realized through the introduction of the chiral NHC catalyst.In the second part,a type of brand-new enantiomerically pure binaphthyl(tert-butylsulfinyl)phosphoramidate catalyst based on(R)-(+)-1,1'-Binaphthy l-2,2'-diol and(S)-(-)-2-Methyl-2-propanesulfinamide skeletons was synthesized.The responding catalysts were explored their catalytic performance in the asymmetric Friedel-Crafts reaction between indoles and imines with a N-Ts group.The reaction proceeded well under mild reaction condition.The preliminary catalytic results showed that the desired product of N-((1H-indol-3-yl)(phenyl)methyl)-4-methylbenzenesulfonamide was obtained in good yield with moderate enantioselectivity.