Msc STEFANOS

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ΕΘΝΙΚΟ ΚΑΙ ΚΑΠΟΔΙΣΤΡΙΑΚΟ ΠΑΝΕΠΙΣΤΗΜΙΟ ΑΘΗΝΩΝ ΣΧΟΛΗ ΘΕΤΙΚΩΝ ΕΠΙΣΤΗΜΩΝ ΤΜΗΜΑ ΧΗΜΕΙΑΣ ΜΕΤΑΠΤΥΧΙΑΚΟ ΠΡΟΓΡΑΜΜΑ ΣΠΟΥΔΩΝ «ΧΗΜΕΙΑΣ» ΕΙΔΙΚΕΥΣΗ «ΑΝΟΡΓΑΝΗ ΧΗΜΕΙΑ ΚΑΙ ΤΕΧΝΟΛΟΓΙΑ» ΕΡΕΥΝΗΤΙΚΗ ΕΡΓΑΣΙΑ ΔΙΠΛΩΜΑΤΟΣ ΕΙΔΙΚΕΥΣΗΣ Κατάλυση της αντίδρασης Stille με νανοσωματίδια Pd σταθεροποιημένα με πολυηλεκτρολύτες παραγόμενους από αμινοξέα ΣΤΕΦΑΝΟΣ ΚΑΡΑΠΕΤΗΣ ΧΗΜΙΚΟΣ ΑΘΗΝΑ
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  1. 1. Stille Pd
  2. 2. 2 2014
  3. 3. 3
  4. 4. 4 Stille Pd ..: 81203 : , 1. . , 2. . , 3. . , 15/10/2014
  5. 5. 5
  6. 6. 6 Pd . () Pd(0) -- o-L- (PNMA), () PNMA-Pd(0) Stille. IR 1 NMR . PNMA-Pd(0) IR TEM SEM, , Pd(0) 1-5 nm. Stille PNMA-Pd(0), . PNMA-Pd(0) , , . , . , . : : Stille, , , .
  7. 7. 7 ABSTRACT The synthesis and characterization of novel Pd nanoparticles is of particular interest in the context of their catalytic applications. In the present dissertation we present (a) the synthesis and characterization of Pd nanoparticles stabilized by the polyelectrolyte poly-N-methacryloyl-L-alanine (PNMA) and (b) the experimental study of the catalytic activity of PNMA-Pd(0) nanoparticles in Stille reactions. The polyelectrolyte was characterized with IR and 1 H NMR spectroscopic techniques. The nanoparticles PNMA-Pd(0) were characterized with IR spectroscopy and, TEM and SEM microscopies, and, it was found that the polyelectrolyte in aqueous solution stabilizes nanoparticles of Pd(0) with 1-5 nm size. We have conducted experiments to investigate the activity of PNMA-Pd(0) in the catalysis of Stille reactions, for seven different aryl halides. The experimental output has shown that PNMA-Pd(0) is an active catalyst in biphasic system, in the absence of organophosphines as auxiliary ligands. The yields of the reactions studied were found to be good to moderate. These results are comparable with recent reports appeared in literature. It was also observed that the reaction yield depends strongly on the nature of the aryl halide, the iodides being more reactive as compared with the bromides. SUBJECT AREA: Nanoparticles for catalysis KEYWORDS: Stille reaction, Catalysis, nanoparticles, palladium.
  8. 8. 8
  9. 9. 9 , , , . , . . Javad Shamandesh .
  10. 10. 10 1. 1 ..................................................................................... 19 1.1 ......................................................................................................... 19 1.2 To ....................................................................... 20 1.3 ........................................................................ 21 2. 2 ................................ 22 2.1 ......................................................................................................... 22 2.2 ................................................ 23 2.3 H Heck...................................................................................... 23 2.4 H Suzuki ................................................................................... 24 2.5 H Negishi .................................................................................. 25 3. 3 STILLE .............................................. 27 3.1 ......................................................................................................... 27 3.2 Stille [11] .......................................... 28 3.3 Stille ..................................... 32 3.3.1 ............................................................................................ 32 3.3.2 Pd(II) Pd(0)...................................................................... 34 3.3.3 ....................................................... 34 3.3.4 .................................................................. 35 3.3.5 (transmetalation).......................................................... 36 3.3.6 ("Copper Effect") ................................................ 37 3.3.7 ...................................................................................... 37 3.4 Stille [3] ...................... 38 3.4.1 ......................................................................... 38 3.4.2 Sanglipherin A ...................................................................... 39
  11. 11. 11 3.4.3 Himastatin............................................................................. 39 3.4.4 Manzamine A........................................................................ 40 4. 4 ................................................................................... 42 4.1 .......................................................................................... 42 4.2 Schwartz.................................................................. 43 4.3 (Pd-black) .................... 44 4.4 ............................... 46 4.5 C-C. ......................... 48 4.6 Stille................. 51 4.7 Pd ............................................................ 54 5. 5 ....................................................................... 57 5.1 ......................................................................................................... 57 5.2 ................................................... 58 5.3 .............................. 60 5.3.1 ........................................................ 60 5.3.2 .......................................................... 61 5.3.3 ....................................................................... 61 5.3.4 .......................................................... 63 5.3.5 .......... 63 5.4 ...................................................... 65 5.4.1 .................................................................................................. 65 5.4.2 ......................................... 65 5.5 ................. 69 5.5.1 .................................................................................................. 69 5.5.2 ................ 69
  12. 12. 12 5.5.3 ............... 70 6. 6 ...................... 71 6.1 ......................................................................................................... 71 6.2 Pd Suzuki . .............................................................................................................. 72 6.3 Pd C-C.................................... 73 6.4 ...................................... 74 6.5 ..................................................................................... 76 6.5.1 ............................................................................................... 76 6.5.2 .......................................................... 76 6.5.3 ............................................................... 77 7. 7 -......................................................... 79 7.1 .............................................................................................. 79 7.1.1 (NMR) .............. 80 7.1.2 (IR) .................................... 80 7.1.3 () ....................................... 80 7.1.4 (SEM) ........................................ 80 7.2 ............................................................................................ 81 8. 8 .................................................................................. 82 8.1 PNMA.................................................................................................................. 82 8.1.1 --L- ()................... 82 8.1.2 --L- ( ).83 8.1.3 PNMA............................................................... 85 8.1.4 --L- (). . 86
  13. 13. 13 8.2 Pd(0) PNMA........................................................................ 88 8.2.1 Pd(0)................................................... 88 8.2.2 Pd(0) ........................................ 89 9. 9 STILLE PNMA-Pd(0)................................................................................................................ 94 9.1 ......................................................................................................... 94 9.2 .................................................................................... 95 9.3 ...................................................................... 95 9.4 ......................................................................................... 102 10. ............................................................................................... 103 ............................................................................................. 122 11. ...................................................... 123
  14. 14. 14 1: ""Pd- 20 . ................................................. 19 2: , ................................................................................... 22 3: C-C. ........................................................................................................... 23 4: Heck. ....................................................... 24 5: Suzuki...................................................... 25 6: Negishi..................................................... 26 7: ........................................................... 27 8: Stille......................................................... 32 9: Stille Espinet. ................ 33 10: (+)-Amphidinolide Stille........................................................................................................................ 35 11: Stille............. 36 12: Cu(I) Stille . .......... 37 13: Rapamycin Nicolaou () Smith ().............................................................. 38 14: - Stille Sangiferin A. ........................................................................................................... 39 15: - Stille Himastatin................................................. 40 16: o Stille Manzamine-A.......................................................................................................... 41 17: Schwartz. ............................................................................................. 43
  15. 15. 15 18: TEM Pd, Stille [C4py][Tf2N] () [C3CNpy]- [Tf2N] (), py= Tf2N = N(SO2CF3)2. , Pd- black. ...................................................................................................................... 44 19: Heck . ........................................... 45 20: PdAS-V PPh3 Pd, . ........................................................................... 47 21: () Pd. () , Ikegami.( ) PdAS-V. ............................................................................................ 47 22: Pd, a) Pd4, b) A6, c) A11, d) A6,11 ................................ 49 23: Stille. ................................................................. 50 24: DEMNs ( )..... 51 25: DEMNs Stille.[66] ................................... 53 26: TMGL ........................................................ 55 27: ................................ 55 28: ILs Heck.................... 55 29: ................................ 56 30: ILs. ................................................ 56 31:TEM (a, b, c) silica (a)20nm,(b)45nm,(c)80nm.SEM(d) (b). silica. .................................... 57
  16. 16. 16 32: . .................................................................................................... 61 33: ......... 62 34: Pd . ................................................................................................. 62 35: Pd ................. 63 36: Pd . ..................................................................................................... 64 37: C-C Pd BINAP. ................................................................................ 64 38: ............................................................... 66 39: . ......................................................................................................... 68 40: MPF. ................................................. 71 41: . ............................... 76 42:) () .................... 77 43: . ............................................... 79 44: , NMA. ............................................................................................................................... 82 45: IR NMA............................................................. 83 46: 1 H-NMR NMA ( CDCl3)..................................... 84 47: IR . ............................................................................. 86 48: 1 H-NMR (D2O)........................................................... 87 49: IR PNMA-Pd(0) 4000-200 cm-1 ().............. 90
  17. 17. 17 50: SEM PNMAPd(0).................................. 91 51: PNMAPd(0).................................... 92 52: PNMA-Pd(0). .......................... 92 53: 1 H-NMR (CDCl3) I-C6H4-H (C6H5-I) Stille (Stille 1) 6,9-7,9 ppm. .................... 96 54: 1 H-NMR (CDCl3) r-C6H4-H (C6H5-I) Stille (Stille 2) 6,9-7,9 ppm. .................... 97 55: 1 H-NMR (CDCl3) CH3-C6H4-I Stille (Stille 3) 6,8-8,0 ppm. .................... 97 56: 1 H-NMR (CDCl3) CH3-C6H4-I Stille (Stille 3) 2,20-2,45 ppm.................. 98 57: 1 H-NMR (CDCl3) CH3O-C6H4-I Stille (Stille 4) 3,70-4,00 ppm.................. 98 58: 1 H-NMR (CDCl3) CH3O-C6H4-I Stille (Stille 4) 6,6-7,0 ppm. .................... 99 59: 1 H-NMR (CDCl3) CH3O-C6H4-Br Stille (Stille 5) 6,6-7,6 ppm. .................... 99 60: 1 H-NMR (CDCl3) I-C6H4-I Stille (Stille 6) 7,2-7,6 ppm. .................................... 100 61: 1 H-NMR (CDCl3) I-C6H4-NH2 Stille (Stille 7) 6,2-7,7 ppm. .................. 100 62: .................................... 101
  18. 18. 18 1: RCOCI R'4Sn. [18] .......................................... 30 2: , Knecht . ...................................................................................... 49 3: Stille 1 H-NMR GC- MS.[66] ..................................................................................................................... 53 4: IR NMA............................... 84 5: 1 NMR NMA..................................................... 85 6: IR . ............................ 87 7: 1 -NMR NMA (D2O). ....................................... 88 8: Stille............. 94 9: Stille, ....................................... 96 10: .............................................................................................. 122
  19. 19. 19 1. 1 1.1 -, , .. Ullmann [1] . , 1990 , . , 2010 (R. F. Heck, E. Negishi, A. Suzuki) "Palladium-Catalyzed Cross Couplings In Organic Synthesis". Pd, . Suzuki, Heck, Negishi, Stille . Suzuki . , Stille ( 1).[2] 1: ""Pd- 20 .
  20. 20. 20 Nobel , . , . , . . 1.2 To (Palladium) 46 106,42. 10 , 5 , 2 . , , 1554,9 C 2963C. Wollaston 1803 "" . , , , . , , : , (.. -C=O, -OH). .
  21. 21. 21 Pd-H Pd-C Pd-X (X=). Pd(II) Pd(0) , . , Ni(0). Rh, Pt Os. . 1.3 Pd . 20-100nm, 1-3 m2 /g. . , .
  22. 22. 22 2. 2 2.1 C-C, , Heck, Stille, Suzuki, Negishi .. : R1 -X + R2 -M R1 -R2 + M-X R1 R2 = -, - -, X = = . PdLn ( 2).[3] 2: , .
  23. 23. 23 2.2 , 3, : 1. (oxidative addition). 2. (transmetalation). 3. (reductive elimination).[4] 3: C-C. 2.3 H Heck Heck, : R-X + R'-CH=CH2 R'-CH=CH-R Pd(0), - HX
  24. 24. 24 Pd(PPh3)4, PdCl2 Pd(CH3COO)2. Heck Pd(0), in situ Pd (II) ( 4).[5] 4: Heck. 2.4 H Suzuki Suzuki : +R1-BY2 R2-X R1-R2 Pd *= : R2 I > R2 OTf > R2 Br >> R2 Cl
  25. 25. 25 5.[6] 5: Suzuki. Suzuki . , , , (.. vancomycin).[7] 2.5 H Negishi Negishi :
  26. 26. 26 Ni Pd, , R R - -. 6.[8] 6: Negishi. Negishi . , Discodermolide , Negishi Pd(0).[9] Pd , .
  27. 27. 27 3. 3 STILLE 3.1 C-C. Stille. - ( 7). 7: . . RSnX4-, ( = 1 4; R = , = , .. , , ). , Sn-C , 200 C. , , Sn-C, :
  28. 28. 28 R. R. , X pH, .[10] 3.2 Stille [11] 1960 .[12] . R-X + Bu3SnH R-X + Bu3SnX To 1973, (u3SnH) (CH2=CHCH2SnBu3) Kosugi , .[13] R-X + CH2=CHCHSnBu3 RCH2CH=CH2 + Bu3SnX Pd, 1976 Eaborn.[14] , .
  29. 29. 29 Pd . Bu3SnSnBu3 +ArBr Pd(PPh3)4 ArSnBu3 + ArAr + Bu3SnBr 1977 [15-17] C-C . C-C . 1978 Stille , PhCH2Pd(PPh3)2Cl, HMPA.[18] Stille : RCOCl + R'4Sn PhCH2Pd(PPh3)2Cl HMPA RCOR' + R'3SnCl 1 Stille .
  30. 30. 30 1: RCOCI R'4Sn. [18] To 1979 [19] . : PhCH2Br + Me4Sn Pd PhCH2CH3 + Me3SnBr 1980 Beletskaya [20] . Guibe .[21] : RCOCl +Bu3SnH Pd(PPh3)4 . RCH=O + Bu3SnCl ,
  31. 31. 31 . . 1984 Stille , .[22] : 1988 Farina , (2-) .[23] , . Stille Pd P(2-furul)3 AsPh3 : , . . , , .. [24] , [25] .[26]
  32. 32. 32 3.3 Stille 3.3.1 Stille .[19] Pd(PPh3)4, Pd(OAc)2, Pd2(dba)3. RSn(R)3 + R'-X Pd R-R' + XSn(R)3 *R,R= , , 8 . 8: Stille. Espinet [27] , 9. , , cistrans, . , .
  33. 33. 33 9: Stille Espinet. Stille, , , [3] . Stille , , . Sn-C. Stille (.. Kumanda, Negishi), (.. Grignard, Zn). stille ( suzuki) Si ( Hiyama). , . , Sn-C . Stille .
  34. 34. 34 3.3.2 Pd(II) Pd(0) Pd(0) in situ Pd(II), (.. PdCl2, Pd(OAc)2 Na2[PdCl4]) , , (.. BuLi). Pd(II) Pd(0) : 1) Et3N 2) PPh3 3) 4) 3.3.3 , , , Stille .
  35. 35. 35 10, (+)- Amphidinolide.[28] 10: (+)-Amphidinolide Stille. 3.3.4 Pd, -, : AsPh3 > P(2-furyl)3 > PPh3 , , /. o L - , .. L=AsPh3, .[28]
  36. 36. 36 3.3.5 (transmetalation) : M1 -R + M2 -R' M1 -R' + M2 -R . , Stille Sn/Pd , . , . 11 , Espinet .[27] 11: Stille.
  37. 37. 37 3.3.6 ("Copper Effect") Stille Cu(I), PdL4 . Farina Liebeskind [29] Cu(I) >102 ( 12).[30] 12: Cu(I) Stille . , - - , Pd, Cu(I).[30] 3.3.7 Stille, Stille Espinet. , , , , , . Pd(0) [31] , [32] [33] C.
  38. 38. 38 3.4 Stille [3] 3.4.1 H . Streptomyces hygroscopicus, . , , Nicolaou, 72 ( 13) Bu3SnCH=CHBu3Sn [PdCl2(MeCN)2] -- (iPr2NEt ) DMF/THF . Stille, Stille 27%.[34] Smith Stille Pd.[35] 13 . 13: Rapamycin Nicolaou () Smith ().
  39. 39. 39 3.4.2 Sanglipherin A Sanglipherin A , . Nicolaou 14.[36] 14: - Stille Sangiferin A. , 86 ( 14) (15 mol%) [Pd2(dba)3]CHCl3, (60 mol%) AsPh3 iPr2NEt DMF 87 ( 14) Stille, 62%. 87 ( 14) Stille 88 ( 14) ( 89). 3.4.3 Himastatin Himastatin . , o Danishefsky Stille
  40. 40. 40 90 ( 15) 91 ( 15), [Pd2(dba)3] AsPh3 DMF 45o C, 92 ( 15) 83%.[37] , , Stille, ( ), .[38] 15: - Stille Himastatin. 3.4.4 Manzamine A H anzamine A , . Martin 16. 109 ( 16) CH2=CHSn(n-Bu)3 [Pd(PPh3)4] 120 C.
  41. 41. 41 110 ( 16), Diels-Alder 111 ( 16) 68%, , Manzamine A.[39] 16: o Stille Manzamine-A. , , Stille . , .
  42. 42. 42 4. 4 4.1 , , . , . Rh Co . : 1. , . 2. , . . . . , . . , , .
  43. 43. 43 . , . , , . 4.2 Schwartz . . Schwartz , .[40] , ( 17). (.. ) (.. - ) (.. ) (..RhClL3) 17: Schwartz. .
  44. 44. 44 4.3 (Pd-black) . Pd ( Pd) Pd-black ( 18). 18: TEM Pd, Stille [C4py][Tf2N] () [C3CNpy] - [Tf2N] (), py= Tf2N = N(SO2CF3)2. , Pd-black. , . Reetz De Vries Heck Pd, Pd-black . [42] , Heck Pd , 19.
  45. 45. 45 19: Heck . . , (.. [42] ) (.. [43] ) , . , , .. (Bu4N+ )/(P2W15Nb3O62 9- ) [44] , , , , . . . , , .
  46. 46. 46 , Reetz, [(C8H17)4N]Br [(C49)4N]Br Pd Pd/Ni, Suzuki Heck.[45] Pd Thompson Pathak [46] Antonieti, -(4-).[47] 4.4 , Rampino Nord 1941.[48] . , Pd 2-8nm, C-C.[49] Pd C-C , -, - - . . , , Pd , .[50-51] , C/ [52] Si/alumina [53] [54] , .
  47. 47. 47 (.. PPh3) . Ikegami PdAS-V ( 20), Pd ( 21). PdAS-V Heck. Heck , PdAS-V , . 20: PdAS-V PPh3 Pd, . 21: () Pd. () , Ikegami.( ) PdAS-V.
  48. 48. 48 Pd . Pd , Pd , . , . Pd [56] .[57] 4.5 C-C. , , . . . , , , . , , C-C. , Stille, Suzuki Heck, , . Pd(0) Pd(II), in situ. (70-100 C) (.. ). Knecht Pd ,
  49. 49. 49 Stille.[58-59] , 24 , 0.0005 mol%. , (Pd4, A6, A11, A6,11) 12 . 1,9 nm 3,7nm ( 2). TEM ( 22). 22: Pd, a) Pd4, b) A6, c) A11, d) A6,11 . 2: , Knecht . (nm) Pd4 TSNAVHPTLRHL 1.90.3 A6 TSNAVAPTLRHL 2.20.4 11 TSNAVHPTLRAL 2.40.5 6,11 TSNAVAPTLRAL 3.70.9
  50. 50. 50 23 Pd, , Stille. Pd() Pd(0) NaBH4.[58] 23: Stille. (H) (). 6 H 6 . 11 H 11, 6,11, 6 11. , , . , , .
  51. 51. 51 4.6 Stille (dendrimers) , 1978 Buchleier.[60] , [61] , [62] .[63] , , [61] . [64] . (.. Pd) (DEMNs=Dendrimers Encapsulated Metal Nanoparticles), 24. [65] 24: DEMNs ( ). () (PAMAM) -- (PPI). H Crooks Pd PAMAM Stille .[66]
  52. 52. 52 . : 1. DEMNs C-C, Heck [67] , Suzuki [68] Stille. 2. T DEMNs Stille , . 3. , . DEMNs, : 1. . , .. CO2.[65] 2. .[65] 3. . Stille : (70o -120o C). (.. ). Pd(0) Pd() in situ Pd(0) Pd(0) . DEMNs Stille .[66] , Stille [69] .[70] . (G4-OH(Pd2+ )40), NaBH4 (G4-OH(Pd40)).
  53. 53. 53 =23 C, Pd. 25 3 , . 25: DEMNs Stille. [66] 3: Stille 1 H-NMR GC-MS. [66]