Iridium-catalyzed Enantioselective Allylic Cyclization Of ?-electron-rich Olefins

This thesis mainly covers the Ir-catalyzed enantioselective allylic cyclization of?-electron-rich olefins and enantioselective allylation of aryl enamides and enecarbamates,including the following three chapters.In chapter one,we discussed the research progress of asymmetric allylation reaction.Nucleophiles were divided into four categories according to the different nucleophilic atoms:carbon,nitrogen,oxygen and sulfur source nucleophiles.Among them,two cases of each type of nucleophile were selected as representatives to discuss its research progress.Since the first Ir-catalyzed asymmetric allylic alkylation reaction was published in 1997,many research groups have explored extensively on this reaction,such as the groups of Hartwig,Carreira and You.Various ligands,promoters,and nucleophiles,etc.have been developed significantly for Ir-catalyzed asymmetric allylation in the past two decades.In chapter two,we discussed the Ir-catalyzed asymmetric allylic cyclization of?-electron-rich olefins.Based on the Carreira's Iridium catalytic system([Ir(cod)Cl]₂ and Carreira ligand),o-amino Boc allyl secondary alcohols or o-hydroxy allylic secondary alcohols were reacted with linear or cyclic?-electron-rich olefin,constructing the heterocyclic systems such as 6/6/5,6/6/6,or hydroquinoline rings with high enantioselectivity.Then,we optimized the reaction conditions,extended the substrate scope and carried out scale-up experiments of this reaction with good regio-and enantioselective products.In the final experimental section,the preparations of allylic secondary alcohol substrates and corresponding products and spectral data of the prodcuts were described.In chapter three,we discussed the Ir-catalyzed asymmetric allylation of aryl enamides and enecarbamates briefly.Based on the same Carreira's Ir catalyst system,allylic secondary alcohols were reacted with N-(1-phenylethenyl)-benzamide and enecarbamate,a newly published method for generating?-allyl-substituted ketones with high regio-and enantioselectivity.