Studies Of Copper-Catalyzed Decarboxylative Coupling Reaction Of ?,?-Unsaturated Carboxylic Acids With CF₃CH₂I Or HP?O??OⁱPr?₂

In the thesis,an efficient Cu-catalyzed stereoselective trifluoroethylation through the decarboxylative cross-coupling of cinnamic acid derivatives with CF3CH2 I is described.A practical Cu(II)-catalyzed decarboxylative C-P cross-coupling of cinnamic acids with diisopropyl phosphonate is achieved.1.Decarboxylative coupling reaction of CF3CH2 I with ?,?-unsaturated acidsA practical and efficient trifluoroethylation through the decarboxylative cross-coupling of cinnamic acid derivatives with CF3CH2 I is described.The optimized conditions was obtained through the combination of 0.4 mmol cinnamic acid,2 equiv CF3CH2 I,40 mol% Cu(OTf)2,2 equiv Ag2CO3,and 3 m L DMSO in the presence of Et3 N at 80 °C under Ar atmosphere for 24 h(Scheme 1).The substrate scope evaluation of the copper-catalyzed decarboxylative trifluoroethylation of cinnamic acids was also achieved.The results shows that the catalytic strategy has good substrate compatibility and excellent chemoselectivity.2.Decarboxylative coupling reaction of HP(O)(OiPr)2 with ?,?-unsaturated acidsA simple and practical strategy to construct C-P bond through decarboxylative coupling reaction of ?,?-unsaturated acids with HP(O)(OiPr)2 has been developed.Through screening catalyst,ligand,additive,solvent,reaction temperature and reaction time,the best reaction condition was achieved with Cu CO3 as catalyst,1,10-phenanthroline as ligand,Ag2 O as additive,DMSO as solvent,110 oC for 12 h(Scheme 2).Under the optimized condition,a variety of alkenylphosphorus derivatives were produced in moderate to good yields.The notable advantages of the protocol are its high yields,and broad functional group compatibility.