Dissertation
Dissertation > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Chemical kinetics,catalysis > Catalytic > Catalytic reaction

Study on Copper Catalyzed C-X (N, O, S) Cross-Coupling Reactions

Author FengYang
Tutor LiYaMing
School Dalian University of Technology
Course Fine Chemicals
Keywords Ullmann reaction copper catalyzed ligand cross coupling reactions
CLC O643.32
Type Master's thesis
Year 2009
Downloads 298
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Formation of C(aryl)-N,C(aryl)-O,C(aryl)-S bonds are important in synthetic organic chemistry stemming from the varity of many compounds containing C-X(N,O,S) bond in pharmaceuticals and polymer materials.In the last decade,copper-catalyzed Ullmann-type cross coupling reactions have become a principle method for organic synthesis.Based on the previous work on copper-catalyzed C-N coupling reaction,copper catalyzed C-S,C-N,C-O coupling reactions were studied.After the optimization of the reaction conditions such as ligands,solvents,copper salts, bases,the ratio of copper to ligand,etc,an efficient catalytic system composed of 20 mol% 1,2,3,4-tetrahydro-8-hydroxyquinoline with 10 mol%CuBr was found.The catalytic system promoted the C-S coupling reaction under 80℃or milder condition.The catalytic system successfully promoted the coupling of aryl iodides and activated aryl bromides with both aryl and aliphatic thiols,and gave isolated yields at 62-99%.Further more,the system which had a good chemoselectivity tolerated various functional groups such as -Ac,-CN,-OMe,-OH, -NH2,-CHO,etc.A possible mechanism for copper-catalyzed C-S coupling reaction was discussed.H acid,a compound with good water-solubility and ecnomic ability,was found as a ligand used for copper-catalyzed C-N coupling reaction in water.CuCl2/H acid/TBAB catalytic system had a certain effect and catalyze the coupling of iodobenzene with benzyl amine with a HPLC yield of 46%.Using CuCl as catalyst,o-aminophenol derivatives were studied as ligands in copper catalyzed C-O coupling reaction.After a series of optimization and experiments,isolated yields of 48-68%were obtained.Further studies on these ligands used in copper catalyzed C-O coupling reaction were needed for the limitation of the structures they had.In conclusion,a mild and efficient catalytic system was developed for copper-catalyzed C-S bond formation.Copper-catalyzed C-N coupling reaction in water and C-O coupling reaction were also studied.

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