Chiral Bipyridine Ligand Synthesis And Copper-Catalyzed Asymmetric Reaction Of Electron-Deficient Olefins

Asymmetric catalysis is an important part of contemporary organic synthetic chemistry,and it is one of the most promising methods for preparing optically active products.Among them,the asymmetric catalysis of metal complexes has attracted wide attention of researchers because of its efficient synthesis process.As the earth-aboundant,cheap and easily available metal,the asymmetric reaction of copper catalysis has become one of the important choices for researchers.Therefore,the continued development of new ligands and copper-catalyzed asymmetric reactions remains a hot topic of research today.This dissertation is mainly focous on design and synthesis of novel chiral bipyridine ligands;and a series of asymmetric copper catalyzed reactions of electron-deficient olefins.The specific research contents include the following four aspects:??Design and synthesis of novel chiral bipyridine ligandsStarting from commercially available dibromopyridine,a series of conversions such as coupling,condensation,and addition provide a new type of tert-butylsulfenamide-derived bipyridine ligand.These chiral ligands have multiple coordination sites,and are expected to have a potential catalytic applications.??Copper-catalyzed synthesis of chiral pyrrole derivativesFirst,a highly chemo-,diastereo-,and enantioselective Cu(1)/(S,S)-Pr-FOXAP catalyzed Michael addition of ketiminoester to ?-trifluoromethyl ?,?-disubstituted enones was developed.This method provides a facile access to highly functionalized 1-pyrrolines bearing two contiguous stereocenters,which including a trifluoromethylated all-carbon quaternary stereocenter via one-pot hydrolytic cyclization.In addition,a catalytic asymmetric[3+2]cycloaddition of glycine ketimines with/3-CF3 ?,?-disubstituted enones was realized in the presence of a chiral copper(I)/Ming-Phos complex.This method provides an access to construct highly functionalized pyrrolidines bearing three contiguous stereocenters,which including a trifluoromethylated all-carbon quaternary stereocenter.Following,when(R)-Tol-BINAP ligand was used,a cycloaddition of indol-derived electron-deficient olefin with azomethine ylide was achieved.Finally,we provides an efficient access to the chiral cyclic 1,2-bis(diphenylphosphines via asymmetric[3+2]cycloaddition.Both enantiomers of the products can be obtained with good to excellent diastereo-and enantioselectivities:??Copper-catalyzed asymmetric boronation of electron-deficient olefinsAsymmetric boration of ?,?-disubstituted electron-deficient enones and B2Pin2 was development under the catalysis of Cu(NO3)2·3H2O/(S,S)-Pr-FOXAP,furnishing high enantioselective compounds containing quaternary carbon center of CF3 and boron atom.In addition,the preparation of the chiral tertiary alcohol was accomplished by one-pot method.The reaction provides a feasible path for the synthesis of highly enantioselective boron-containing compounds.??Copper catalyzed asymmetric tandem cyclization to indene DerivativesThis method provides access to multi-substituted indanes holding three consecutive chiral centers via Michael addition/Aldol cyclization.The features of this reaction include high enantioselectivity,easily prepared starting materials,well functional group tolerance and mild reaction conditions.