Nickel-catalyzed Reductive Coupling Of Unactivated Tertiary Alkyl Halides With Aryl Halides

The dissertation introduces mainly Nickel-catalyzed reductive coupling of unactivated tertiary alkyl halides with aryl halides to construct ary quaternary stereocenters,including several aspects below:1,Importance of quaternary stereocenters in natural products and some progress on metal-catalyzed reaction on the synthesis of quaternary stereocenters.2,Nickel-catalyzed reductive coupling of unactivated tertiary halides with aryl bromide substituted by electron-withdrawing groups under mild condition.In the present of Ni?acac?₂ as catalyst,Zn as reductant,MgCl₂ and iPr-Im-HCl as additives,DMAP as ligand,and DMA as solvent,we had realized the coupling of a variety of tertiary alkyl halides with aryl bromides substituted by electron-withdrawing groups.3,Nickel-catalyzed reductive coupling of unactivated tertiary halides with aryl iodides substituted by electron-donating group.In the present of Ni?acac?₂ as catalyst,Zn as reductant,MgCl₂ and LiCl as additives,3-F pyridine as ligand,and DMA as solvent,we had realized the coupling of a variety of tertiary alkyl halides with aryl iodides substituted by electron-donating groups.4,Mechanism on coupling of tertiary alkyl halides with aryl halides was investigated.We had isolated the intermediate compound,and made a variety of control experiments.With the help of DFT,we revealed the affection of additives,such as DMAP,MgCl₂,change of intermediate compounds,and proposed a mechanism of this reaction,systematically.