Nickel-Catalyzed Redox-neutral Coupling Reactions Of Alkynes And Allyl Alcohols

Transition metal catalysis has extensively investigated during the past few decades,especially nickel-catalysis,which has been applied to the synthesis of active pharmaceutical ingredient and functional materials.Alkynes as a bulk feedstock chemicals,which are important building blocks in synthetic organic chemistry and organic synthesis.Unlike the noble metal catalyzed,diverse functionalization reactions with alkynes,the earth-abundant nickel-catalysis has received more and more attention in these reactions.In this thesis,we reported the synthesis ofγ,δ-unsaturated ketones from commercially available allyl alcohol and alkynes with Ni-catalysis.Using diphenyl acetylene and oct-1-en-3-ol as model substrates,the reaction parameters,like nickel catalyst,ligand,reaction temperature and concentrations,were evaluated.Finally,the combination of nearly equal proportions of alkyne and allyl alcohol,Ni（cod）₂ and SIMes·HCl furnished the synthesis ofγ,δ-unsaturated in high yields in one pot.The reaction proceeds through an redox-neutral pathway and no external reductant was needed.Good compatibility for allyl alcohol substituted with alkyl or aryl.There is good tolerance to alkynes,alkyl-substituted or diarynes with different substituted groups,and possible reaction mechanisms were proposed.In conclusion,this paper presents a methodological study of the redox-neutral coupling reactions of alkynes and allyl alcohols using commercially available nickel catalysts,commercially available or ingredients that can be simply synthesized.Compared with the conventional method of constructingγ,δ-unsaturated ketones,with the characteristics of high atomic utilization rate,mild conditions,simple operation and good universality,it is a general method to constructγ,δ-unsaturated ketones.