Study On Allylation And Conversion Via The Cleavage Of C-O Bond Of Allylic Alcohols Or C-N Bond Of Allylamines

This thesis mainly focuses on allylation and conversion reactions through C-O bond cleavage of allyl alcohols or C-N bond cleavage of allylamines,including(1)synthesis of 1,4-enyne derivatives through nickel catalyzed C-O bond cleavage of allyl alcohols;(2)Ruthenium catalyzed C-H aminoallylation and its further conversion to indole derivatives;(3)Transition-metal-free transformation of allylamines via C-N bond cleavage to allylated arylamines.Moreover,synthesis of Indoles through palladium-Catalyzed N-Arylation of Indoles with Nitroarenes.Chapter 1 summarizes the research progress of allylation reaction via C-O bond cleavage of allylic alcohols and their derivatives and C-N bond cleavage of allylamines,including synthesis of 1,4-enynes by allylation reaction via C-O bond cleavage of allylic alcohols and their derivatives,and construction of heterocyclic compounds by allylation and cyclization reaction with C-O bond cleavage of allylic alcohols and their derivatives,as well as allylation reaction via C-N bond cleavage of allylamines.Chapter 2 is about synthesis of 1,4-enynes using allylic alcohols as allylation reagents.Under NiCl2(dppe)catalyst the cross coupling reaction of allylic alcohols with alkynylzinc reagents effectively proceeds to achieve 1,4-enynes.The protocol exhibits high regio-and Z/E-selectivity.The coupling reaction of(E)-3-arylprop-2-en1-ols or 1-arylprop-2-en-l-ols with alkynylzinc reagent results in only linear 1,4-enynes products.Moreover,the coupling reaction exhibits good functional group compatibility.F,Cl,OMe,OPh,SMe,NMe2,CF3,COOEt and C(O)NEt2 groups as well as benzothiophene,thiophene and furan rings are tolerated.The mechanistic studies indicate that the coupling reaction of allylic alcohols with alkynylzinc reagent might proceed through a catalytic cycle of Ni(0)/Ni(Ⅱ).Chapter 3 reveals ruthenium(Ⅱ)-catalyzed reaction of allylamines with aniline derivatives to construct 2-methylindoles.The method employs 4,5-dimethylpyrimidin-2-yl as the directing group,does not require external oxidants and can tolerate various functional groups such as F,Cl,Br,OMe,CF3,OCF3,OCHF2,CH3C(O),CO2Et,C(O)NMe2,C(O)NHMe,SO2Me,CN,and NO2 groups as well as nitrogen-containing and oxygen-containing heterocycles,allowing a broad range of aniline derivatives to undergo site-selective synthesis of indole derivatives.The mechanistic study shows that the reaction process may include C-H bond activation,twice β-H elimination,cyclization,C-N bond activation,and double bond isomerization steps.Chapter 4 introduces the aza-Claisen rearrangement of allylamines to achieve allylated arylamines.The reaction is metal-catalyst-free and can proceed smoothly when heated in trifluoroethanol,leading to allylated arylamines in good yields.It does not require the presence of proton acid or Lewis acid,nor does it need to convert allylamines into corresponding quaternary ammonium salts prior to the rearrangement.Chapter 5 describes Pd(acac)2/Brettphos-catalyzed N-arylation of indole derivatives using nitroarenes as the electrophiles,affording a series of N-aryl indoles.The electron-donating and electron-withdrawing nitroarenes can be employed as the electrophilic species.The N-arylation reaction of two bioactive indoles were also carried out,which fully exhibits the utility of this method.