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指導教授 : 于淑君 博士 2013 / 07

Synthesis and Characterization of Aminodipyridylphosphine Oxide Iron(II) Complexes. Catalytic Application on Microwave-Assisted Amidation of Aldehydes. 指導教授 : 于淑君 博士 2013 / 07 . 學 生 : 蔡俊偉. Green Chemistry. 能源的綠色化  提升能源的效率如微波. 化學反應的綠色化  原子 經濟反應. 原料的綠色化  無毒無害的原料  可再生資源.

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指導教授 : 于淑君 博士 2013 / 07

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  1. Synthesis and Characterization of Aminodipyridylphosphine Oxide Iron(II) Complexes. Catalytic Application on Microwave-Assisted Amidation of Aldehydes 指導教授: 于淑君 博士 2013 / 07 學 生: 蔡俊偉

  2. Green Chemistry 能源的綠色化 提升能源的效率如微波 化學反應的綠色化 原子經濟反應 原料的綠色化 無毒無害的原料 可再生資源 產品的綠色化 環境友好產品 觸媒的綠色化 無毒無害的觸媒 溶劑的綠色化 無毒無害的溶劑 Chahbane, N.; Popescue, D., L.; Mitchell, D., A.; Chanda, A.; Lenoir, D.; Ryabov, A.D.; Schramm, K., W. and Collins, T., J. Green Chem. 2007, 9, 49–57.

  3. Green Catalysts • Solid acid catalysts • Ex, Nafion-H, SO42-/ZrO2、SO42-/TiO2, … • HPA catalysts • H3PMo12O40,H4PW11VO40 • Zeolite catalysts • ZSM-5, X-type, Y-type • Metal catalysts • heterogeneous catalysis, homogeneous catalysis • Enzyme Sheldon, R., A.; Arends, I., W.,C., E.; and Hanefeld, U. (2007) Green Chemistry and Catalysis, Wiley-VCH VerlagGmbH, Weinheim

  4. Application of Green Chemistry epoxidation Anilkumar, G.; Bhor, S.; et. al. Tetrahedron Asymm., 2005 , 16, 3536–3561 Sonogashira coupling Hasan, K.; Browne, N. and Kozak, C.,M. Green Chem., 2011, 13, 1230.

  5. PhosphineLigand • Phosphines are electronically and sterically tunable. • Chemical waste - water bloom • Air/water sensitive and thermally unstable. • Metal leaching. • . Expensive. 5 Kinzel, E. J. Chem. Soc. Chem. Commun.1986 1098.

  6. The importance of Fe(II) • Iron is one of the most abundant metals on earth. (5.6% of earth’s crust. 4th most abundant element after oxygen, silicon, and aluminum. • Iron is environmentally friendly metal • low toxic • In body play a important role to transport oxygen (woman 2.5g ， man 4g) 60 mg/kg to iron poisoning

  7. The Catalytic Applications of Fe(II) • Ring Opening Reactions • Kharasch Reaction • Cross-Coupling Reactions • Mukaiyama-aldol reaction • Cycloadditions • [2+1]-Cycloadditions • [2+2]-Cycloadditions • Acetalization • Diels-Alder Reaction • Sulfide Oxidations • Aminochlorination • AllylicAminations • Baeyer-Villiger Reactions • Amidation Reaction

  8. Amide Bond C. A. G. N. Montalbetti, V. FalqueTetrahedron , 2005,61, 10827–10852

  9. Applicationof Acyl Sulfonamides HCV NS5B polymerase allosteric inhibitors antitumor activity Navitoclax Hepatitis C Virus Non-structural protein 5B, NS5B S. Jana, F. Hof. J. Org. Chem. 2011, 76, 3733–3741

  10. Acyl Sulfonamides J. Chan,* K. D. Baucom, and J. A. MurryJ. Am. Chem.Soc. 2007, , 129, 14106-14107 J. W. W. Chang and P. W. H. Chan*Angew. Chem. Int. Ed. 2008, 47, 1138-1140 J. W. W. Chang and P. W. H. Chan*J. Org. Chem. 2011, 76, 4894-4904

  11. Motivation • Well-defined structure • Iron is environmentally friendly metal • Iron is less expensive than other transition metals. • - Rh2(esp)2$30172 USD/mol ReagentPlus® (Aldrich) • - Ru(TTP)CO$20740 USD/mol reagent grade (Sigma-Aldrich) • - FeCl2.4H2O$148 USD/mol reagent grade (Sigma-Aldrich) • Using bipyridineligandto replace phosphineligand in organomatallic catalysis. • Microwave to replace thermal energy

  12. Synthesis of 4C-Ppy2 and (4C-Ppy2)2FeCl2 80 % 80 % 80 % IR (KBr) : py Ring stretching = 1590(s), 1426(s) cm-1

  13. IR Spectra of 4C-Ppy2 and (4C-Ppy2)2FeCl2 νC－C (Py ring) νC－N (Py ring) a. b. Hahn, F. E.; Langehahn, V.; Lügger, T.; Pape, T.; Le Van, D. Angew. Chem. Int. Ed. 2005, 44, 3759-3763. Zerong, L.; Zhongquan, L.; Ning, M. and Biao, W. Bull. Korean Chem. Soc.2011, 32, 2537-3543

  14. Iron Complexes –Catalyzed Amidation Reactions of Aldehyde with PhINTs

  15. AASpectrum of [CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2 Calculated base on chemical formula AAdata 2.48710-6mol/mg Fe 1.46710-6mol/mg Fe experimentalAA data

  16. Colorimetryof [CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2 max = 510nm Fe2+ + 3phen  (phen)3Fe(II) 1,10-Phenanthroline Visible spectrum of (phen)3Fe(II) Harvey, J.; Aubrey, E.; John, A. Smart, Analytical Chemistry1955, 27, 26-29.

  17. ESI-MS Spectrum of [CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2 [CH3(CH2)3N(H)P(O)(2-py)2]FeCl2+= 401(m/z) [CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2+= 676(m/z) SimulatedMS Data SimulatedMS Data ExperimentalMS Data ExperimentalMS Data

  18. EPR Spectrum of [CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2 g = 2.199 g = 2.04 (radical) 300 k, MeOH 77 k, MeOH Li Zhong-Fang, et al. Chinese Journal of Inoranic chemistry2003, 19.7, 691-698.

  19. Synthesisof 11C-Ppy2 93 % 80 % Lin, Y.-Y; Tsai, S.-C.; Yu, S. J. J. Org. Chem.2008, 73, 4920-4928.

  20. Synthesis of (11C-Ppy2)2-FeCl2 IR (KBr) :  py Ring stretching = 1588(s), 1425 (s) cm-1

  21. IR Spectra of 11C-Ppy2 and (11C-Ppy2)2-FeCl2 1575cm-1 T( %) 1424cm-1 νC－C (Py ring) 1588cm-1 νC－N (Py ring) 1426cm-1 Wavenumber

  22. AASpectrum of [HO(CH2)11N(H)P(O)(2-py)2]2FeCl2 Calculated base on chemical formula AAdata 1.106  10-6mol/mg Fe 1.937  10-6mol/mg Fe experimentalAA data

  23. Colorimetryof [HO(CH2)11N(H)P(O)(2-py)2]2FeCl2 max = 510nm Fe2+ + 3phen  (phen)3Fe(II) 1,10-Phenanthroline Visible spectrum of (phen)3Fe(II) Harvey, J.; Aubrey, E.; John, A. Smart, Analytical Chemistry1955, 27, 26-29.

  24. ESI-MS Spectrum of [HO(CH2)11N(H)P(O)(2-py)2]2FeCl2 [HO3(CH2)11N(H)P(O)(2-py)2]2FeCl+= 869(m/z) SimulatedMS Data ExperimentalMS Data 24

  25. Optimization of Reaction Conditions 5 mol % b. no cat.

  26. Reaction ConditionsScreening P＊AB=QAP＊A+QBP＊B

  27. 4C-Ppy2-Fe(II)Complex –Catalyzed Amidation Reactions of Aldehyde with PhINTs General reaction conditions: Aldehyde (1 equiv.), PhINTs(1.5 equiv.), Catalyst (0.05 equiv.) Solvent = 0.67 mL, 40 oC, 3 h. a Yields were determined by 1H-NMR. b. PhINTs = 2 equiv. c 18 h

  28. 11C-Ppy2-FeCl2Complex –Catalyzed Amidation Reactions of Aldehyde with PhINTs General reaction conditions: Aldehyde (1 equiv.), PhINTs(1.5 equiv.), Catalyst (0.05 equiv.) Solvent = 0.67 mL, 40 oC, 3 h. a Yields were determined by 1H-NMR. b. PhINTs = 2.0 equiv.

  29. Summary of Fe(II) catalytic Activity General reaction conditions: Aldehyde (1 equiv.), PhINTs(1.5 equiv.), Catalyst (0.05 equiv.) Solvent = 0.67 mL, 40 oC, 3 h. a Yields were determined by 1H-NMR. b. PhINTs = 2.0 equiv.

  30. Proposed Mechanism of AmidationReactions of Aldehyde with PhINTs J. W. W. Chang and P. W. H. Chan*J. Org. Chem. 2011, 76, 4894-4904

  31. MicrowaveAssisted Amidation Reactions of Aldehyde with PhINTs

  32. Optimization of Reaction Conditions under Focused Microwave

  33. (4C-Ppy2)2-Fe(II) Complex Catalyzed Amidation Reactions of Aldehyde with PhINTs a Yields were determined by H-NMR. Reaction conditions: aldehyde = 0.2 mol (1 equiv.), PhINTs (1.5 equiv.), catalyst (0.05 equiv.), solvent CHCl3 = 0.4 mL.bPhINTs (2.0 equiv)

  34. Summary of Fe(II) catalytic Activity under Focused Microwave a Yields were determined by H-NMR. Reaction conditions: aldehyde = 0.2 mol (1 equiv.), PhINTs (1.5 equiv.), catalyst (0.05 equiv.), solvent CHCl3 = 0.4 mL.bPhINTs (2.0 equiv)

  35. Synthesis of the RS-Au-L1-FeCl2 RS = CH3(CH2)7SH Au-RS RS-Au-L1-FeCl2 RS-Au-L1

  36. IR Spectra of L1 ,Au-L1 and Au-L1-FeCl2 1585cm-1 1428cm-1 1575cm-1 1422cm-1 T (%) 1575cm-1 1426cm-1 Wavenumber

  37. TEM Image of RS-Au-L1-FeCl2 • RS-Au-L1 Fe Particle size distribution2.68 ± 0.3 nm Particle size distribution7.32 ± 1.2 nm

  38. RS-Au-L1-FeCl2 Complex –Catalyzed Amidation Reactions of Aldehyde with PhINTs 30 %

  39. Summary 1.We have success fully synthesized green catalysts [4C-Ppy2]2-FeCl2、 [ 11C-Ppy2]2-FeCl2 .Their Structure were studied by IR, ESI-MS, AA,EPR spectroscopies 2.We have successfully demonstrated the catalytic activity of the Fe(II) complexes for amidation reactions of aldehyde with PhINTs. 3. The Fe(II)-catalyzed amidation reactions of aldehyde with PhINTs can be further accelerated under microwave irradiation conditions.

  40. 620 W 300 oC6格 1.3格 130W

  41. (11C-Ppy2)2-Fe(II) ComplexCatalyzedAmidation Reactions of Aldehyde with PhINTs a Yields were determined by H-NMR. Reaction conditions: aldehyde = 0.2 mol (1 equiv.), PhINTs (1.5 equiv.), catalyst (0.05 equiv.), solvent CHCl3 = 0.4 mL.bPhINTs (2.0 equiv)

  42. Reported Fe(II) Complex –Catalyzed Amidation Reactions of Aldehyde with PhINTs J. W. W. Chang and P. W. H. Chan*J. Org. Chem. 2011, 76, 4894-4904

  43. Reproposed Mechanism of Amidation Reactions of Aldehyde with PhINTs J. W. W. Chang and P. W. H. Chan*J. Org. Chem. 2011, 76, 4894-4904

  44. non classed Staudinger reaction mechanism

  45. Staudinger reaction mechanism

  46. 25 mL 211.5 USD 100 mL 31.9 USD 25 G 396 USD 10G 135.5USD

  47. 理論值 =0.0002 mol*0.05 = 0.00001mol0.00001*55.845/15.584´10-4g (in 1ml )

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