Study On Activation Of Inert Bonds Catalyzed By Copper Or Rhodium

1.Study of the reaction of cyclobutanone oxime ether C-C bond activation catalyzed by copperDicyanaphthene cyanogen is a kind of important intermediate in medicine and dyestuff.Currently,most of the reported synthesis methods of such compounds use highly toxic cyanide.We synthesized dicyanaphthalene cyanide compounds by copper catalyzed activation of C-C bond of cyclobutanone oxime ether in a simple,low-toxic and efficient way.The reaction system took cyclobutanone oxime ether as the substrate,Cu(OTf)2 as the catalyst and THF as the solvent,and a total of 17 substrates were examined.The reaction mechanism was covered by TEMPO capture,competitive experiment and photocatalytic exploration,and the possible reaction mechanism was proposed based on the experimental results.Three of the products were studied in this paper.All the new compounds were characterized by IR,1H NMR,13C NMR and HRMS.2.Study of the reaction of Alkenyl trifluoromethyl C-F bond activation catalyzed by copperFluorinated drug is a kind of drug molecule with special pharmacological activity.It is a great challenge to design and synthesize new fluorinated compounds.Currently,the synthesis of fluorinated compounds is mostly to construct C-F bonds.Our idea is to build new fluorinated compounds by activating and breaking C-F bonds We took enyl trifluoromethyl as the substrate and reacted with the format reagent under the catalysis of copper to complete the defluorination alkylation.The reaction used CuBr as catalyst,quivalent sodium phenol as base,nitrogen carbene ligand coordination,toluene as solvent,a total of 16 substrates were examined.For the reaction products,we also carried out a further study,extending the other conversion of the obtained compounds.All the new compounds were characterized by IR,1H NMR,13C NMR,19F NMR and HRMS.3.Rhodium-catalyzed C-H bond activation of indoles C7Indole ring is an important structural unit of drug and natural products.Indoles C2 and C3 C-H bond activation reactions have been reported in many literatures,while C-H bond activation in benzene ring region is relatively difficult.Therefore,the development of C-H bond activation in benzene ring region has become one of our main goals.We use ditert-butyl phosphonindole as substrate,Rh(COD)2OTf as the catalyst,anhydride as the activation reagent,and toluene as the solvent,and reacted with enyl carboxylic acid at 120? to achieve alkenylation of indoles C7,a total of 26 substrates were examined.The structure was also determined by X-ray diffraction.Under the condition of TBAF and 60?,the direct group ditert-butyl phosphine was successfully removed after stirring for 24h,and a high yield was obtained.According to the literature investigation,we proposed the possible mechanism.All the new compounds were characterized by IR,1H NMR,13C NMR,31P NMR and HRMS.