| In this thesis, the synthesis of a series of palladium(Ⅱ) complexes with2-arylnaphthoxazoles and their applications in Suzuki and Heck reactions werestudied in the following aspects.1. Cyclopalladated ferrocenylimine catalyzed Suzuki cross-coupling reactions toafford ortho-substituted biarylsThe application of cyclopalladated ferrocenylimines 1 and 2 in the coupling of arylhalides with 2-methoxy-1-naphthylboronic for the synthesis of ortho-substitutedbiaryls was studied. We found that the air-and moisture-stable triphenylphosphineadduct of cyclopalladated ferrocenylimine 2 was an efficient catalyst in the Suzukicross-coupling for synthesis of ortho-substituted biaryls in air. In the presence of 0.05mol% of 2 as catalyst and 3 equiv, of CsF as base in dioxane at 100℃,ortho-substituted biaryls were synthesized with moderate to high yields in thereactions of aryl halides with 2-methoxy-1-naphthylboronic acid. Fourteen newortho-substituted biaryls 5b-5j, 5n, 50, 5q-5s were obtained and characterized by IR,NMR, elemental analysis and MS spectra.ArX=C6H5Br(a),4-CH3C6H4Br(b),4-CH3OC6H4Br(c),4-N(CH3)2C6H4Br(d),4-CH3OCC6H4Br(e),4-ClC6H4Br(f),4-NO2C6H4Br(g),4-CNC6H4Br(h),4-CF3C6H4Br(i),3-CHOC6H4Br(j),2-CH3C6H4Br(k),2,6-(CH3)2C6H3Br(l),C10H7Br(m),2-BrC5H4N(n),3-BrC5H4N(o),2-BrC4H3S(p),2-BrC4H3S(q),4-NO2C6H4Cl(r),3-NO2C6H4Cl(s),2,4-(NO2)2C6H3Cl(t) 2. Synthesis of 2-arylnaphthoxazoles promoted by triethylamineA variety of 2-arylnaphthoxazoles were successfully synthesized in moderate tohigh yields by the reaction of aromatic aldehydes with 1-amino-2-naphthol derivativesin the presence of triethylamine in refluxing ethanol in air. Eight new2-arylnaphthoxazoles 8f, 8j, 8m, 8n, 8o, 8s, 8t and 8u were obtained andcharacterized by IR, NMR, elemental analysis and MS spectra. In addition, the X-raycrystal structures of 8d, 8n and 80 were determined.R1=HCl,R2=HAr=C6H5(a),4-CH3C6H4(b),4-CH3OC6H4(c),4-N(CH3)2C6H4(d),3,4-(CH3O)2C6H3(e),3-BrC6H4(f),4-NO2C6H4(g),2-NO2C6H4(h),2-HOC6H4(i),2-CH3OC6H4(j),2-CHOC6H4(k),2-Furan(l),2-Pyridinyl(m),Ferrocenyl(n),1,1'-Ferrocenediyl(o)R1=—,R2=SO3HAr=C6H5(p),4-CH3OC6H4(q),2-HOC6H4(r),2-Furan(s),2-Pyridinyl(t),Ferrocenyl(u)3. Synthesis of palladium(Ⅱ) coordinated compounds with 2-arylnaphthoxazolesSeven air-and moisture-stable new palladium (Ⅱ) coordinated compounds 9a-9c, 9i,9m, 9q and 9r were synthesized and characterized by IR, NMR, elemental analysisand MS spectra. The structures of 9c and 9i were determined by single-crystal X-rayanalysis. It was found that there are five- and six-membered rings in the complexes9a-9c, 9m, 9q and 9i, 9r, respectively. 4. Palladium (Ⅱ) coordinated compounds 9a-9c, 9i and 9m as phosphine-freecatalysts for the Heck reactionPalladium (Ⅱ) coordinated compounds 9a-9c, 9i and 9m were applied as efficientphosphine-free catalysts for the Heck reaction with aryl bromides and ethyl acrylate.Typically, without the protection of inert gas, in the presence of 2 equiv, n-Bu4NBr,using 0.01% of 9c as catalyst and 2 equiv, of K2CO3 as base in DMF at 140℃provided coupled products in moderate to high yields.ArBr=C6H5Br,4-CH3C6H4Br,4-CH3OC6H4Br,4-N(CH3)2C6H4Br,4-ClC6H4Br,4-CF3C6H4Br,3-CHOC6H4Br,2-CH3C6H4Br,2,6-(CH3)2C6H3Br,Cl10H7Br,2-CH3C10H6Br,2-BrC5H4N,3-BrC5H4N,2-BrC4H3S,2-BrC4H3S 5. Water-soluble palladium (Ⅱ) coordinated compounds 9q and 9r asphosphine-free catalysts for the Suzuki coupling in aqueous solventsWater-soluble palladium (Ⅱ) coordinated compounds 9q and 9r were applied asefficient phosphine-free catalysts for the Suzuki coupling reaction with aryl bromidesand phenylboronic acid in water. Typically, without the presence of phosphine ligand,using 0.1% of 9q as catalyst and 2 equiv, of K3PO4 as base in water at 100℃provided coupled products in moderate to high yields.Synthesis and structural characterization of new 2-ferrocenylnaphthoxazolemercurated derivativesTwo mercurated derivatives [HgCl{(η5-C5H5)Fe[(η5-C5H3)C(O)=N(C10H6)]}] (10)and [HgCl{(η5-C5H4)Fe[(η5-C5H4)C(O)=N (C10H6)]}] (11) were obtained by thereaction of 8n with mercuric acetate. Both the new compounds were characterized byelemental analyses, IR, NMR, MS spectra. In addition, the X-ray crystal structure of10 was determined.
|
PDF Full Text Request