yukikinzoku-koshu

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yukikinzoku-koshu

  1. 1. 1s3+2s1s2sLi Li+e -Li1s2s
  2. 2. 1s: + 2.72s: + 1.31s: + 32s: + 31s: + 32s: + 13+3+Li1s2s3+ 1s2s←LiLi
  3. 3. Li Be B C1s2s2px 2py 2pz3s3px 3py 3pz1s2s3s1s2s3s1s2s3s3px 3py 3pz3px 3py 3pz3px 3py 3pz2px 2py 2pz2px 2py 2pz2px 2py 2pz
  4. 4. H HΔEb1s 1s1
  5. 5. HeΔEbΔEaΔEa >ΔEb
  6. 6. 1s2sH Liδ- δ+H Liδ- δ+H OHH2 + LiOH32.11.0
  7. 7. H Liδ- δ+H Clδ-δ+1.02.13.02.1
  8. 8. sp32s2sp3Li Cδ+ δ-HCLi HHδ+δ-CLi
  9. 9. vsEbE = Ea + EbEiA B+ -A Bδ+ δ-E = Ei
  10. 10. EaEbE = Ea + Eb= Ei + 2EbEi EiEbLi CLi+ C-Li2sC2sp3C2sp3Li2se-CLi
  11. 11. 1 3CH3CH2CH2CH2 LiCH3CH2CHCH3LiCH3C CH3LiCH3n-BuLis-BuLit-BuLiCH3 Libutyllithium methyllithiumLiphenyllithium
  12. 12. CH3CH2CH2CH2 LiCH3CH2CHCH3Li CH3C CH3LiCH3n-BuLi s-BuLi t-BuLi< <CH3C CH2CH3LiHδ+δ- CH3C CH2CH3LiH
  13. 13.   Bu Li R H+ Bu H R Li+Bu LiR RCO+R RCOLiBu
  14. 14. 11.Br + 2Li Li + LiBr+ 2Li + LiBrBr Li2THF
  15. 15. 22.H + n-BuLi Li Bu H+O+ n-BuLiO Li+ C4H10
  16. 16. R Hn-BuLiR LiCH3OH n-BuLiCH3OLiBu H+Bu H+
  17. 17. 33.Brn-BuLiLiether+ BuBr+Br n-BuLi LiTHFBu Br+Bu+ LiBrTHF
  18. 18. Br n-BuLi Liether+ BuBrBr n-BuLi LiTHFBu Br+Bu+ LiBr
  19. 19. 33.+ BuBrO+ n-BuLiOBr Li
  20. 20. n-BuLi s-BuLi t-BuLiEt2O 6THF0 30-30OBu Li H OLi OLi
  21. 21. LiH3CCH3H3CLiLiLiH3C THFTMEDA(R–Li)n (R–Li)2-4/ pentane / THFNMe2Me2NTMEDALiRLiRNNNN
  22. 22. R Li + Cl SiR3 R SiR3 + LiClR Hn-BuLiR LiBu H-ZnCl2R ZnCl- LiClLi:1.0, Si:1.8, Zn:1.6
  23. 23. 2Li CH3+OHH HHH3C OLi H3O+HHH3C OH
  24. 24. C O π∗H3CLiδ-Li CH3+OHH HHH3C OLiLUMO.LUMO
  25. 25. 11 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18H HeLi Be B C N O F NeNa Mg Al Si P S Cl ArK Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br KrRb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I XeCs Ba La Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At RnFr Ra Ac
  26. 26. 11HLiNaKRb2.21.00.90.80.7
  27. 27. EbEiEbM Cδ+ δ-EiEbM Cδδ+ δδ-M+ C- CM
  28. 28. M+ C- CMMe Na Bu K ×H H + Na H Na + 0.5 H2+ Na Na+Sodium acetylideSodium naphthalenideliq. NH3e-
  29. 29. 1s2s2px 2py 2pz3s3px 3py 3pz1s2s2px 2py 2pz3s3px 3py 3pzMgNaNa+ Mg2+
  30. 30. 1912F. A. Grignard (1871-1935)GrignardBr Mg CH2CH3
  31. 31. R Br + Mg R MgBrTHF or Et2O
  32. 32. 1s2s2px 2py 2pz3s3px 3py 3pz3sp32sp3HCMg HHδ-Brcf Li: 1.0δ+
  33. 33. MgBr HH OHδ+ δ−δ+δ−
  34. 34. GrignardRX + Mg RX + MgI R + X- + MgIR Mg XR R1/2
  35. 35. GrignardXMgMgXRR Mg XR2 R2Mg + MgX2XMgMgXRRSchlenk
  36. 36. 1s2s2px 2py 2pz3s3px 3py 3pzsp2MgR BrMgR BrMgRBrXMgMgXRRMg XR2Mg
  37. 37. GrignardBr Mg MgBrOPh OMgBrH3O+ Ph OH
  38. 38. GrignardMg XRR1 R2O+R1R2O MgRXMg XRR1R2O MgRXMgXRR1 R2R O XMg XR+
  39. 39. LUMOR RO+RRORRORROnππ∗Nu-R RNu O-Nu-π∗(LUMO)LUMO
  40. 40. Mg XRR1 R2O+R1R2OMgRXRRORRORROnππ∗RRORRORROnππ∗MgXRδ+π*
  41. 41. C OC Oππ∗C CC Cππ∗HF/3-21G (Gaussian 03)
  42. 42. LUMOMg XRR1 R2O+R1R2O MgRXMg XRR1R2O MgRXMgXRR1 R2R O XMg XR+
  43. 43. RMgX + SiCl4 R4Si + 4MgX2ArMgX + PdCl2L2 Pd LClArL+ MgX2
  44. 44. 1s2s2px 2py 2pzB2px2sp22pxBB C2sp2B Cδδ+ δδ-B CLi(1.0), Mg(1.2)
  45. 45. B2pxRH BRRHBRRR δ+δ−RBR2HROHHH2O2NaOHR H+ RH+H2O RH+H2ORHOH-H+anti-MarkovnikovMarkovnikovcf.
  46. 46. 2sp2B Cδδ+ δδ-B CLi(1.0), Mg(1.2)B PhHOHOB CHOHOB CHOHOB EtEtEt
  47. 47. LiB(OMe)3Li+-BOMeOMeOMe B(OH)2H3O+HBR2BR2HHBR2
  48. 48. •  13• 
  49. 49. XBR2XROBR2+BR2H ROROHH2O
  50. 50. LUMOMg XRR1 R2O+R1R2O MgRXMg XRR1R2O MgRXMgXRR1 R2R O XMg XR+
  51. 51. 6ROBR2+ RCHOBR2 COBR2RHBR2πCOBR2COπ∗COBR2RH
  52. 52. Suzuki–MiyauraB(OH)2B(OiPr)2XX = Cl, Br, I+PdXB(OH)2+Br Pd(PPh3)4, NaOEtEtOH+87%Z ZZZ
  53. 53. : Al (1.5), C(2.5)Li (1.0), Mg (1.2), B (2.0)Al Cδ+ δ-←Al C
  54. 54. 1s2s2px 2py 2pz3s3px 3py 3pz1s2s2px 2py 2pz 3sp3BAl
  55. 55. AlH3CAlCH3CH3CH3H3CH3CAlCH3H3CH3CAlH3CCH3CH3+AlH3CAlCH3CH3CH3H3CH3CEt2O AlCH3H3CH3COAlCH3H3CH3CO RRRCOR
  56. 56. Et3AlMe3AlBu2AlHEt2AlCl
  57. 57. LAH DIBALO LiAlH4 (LAH)iBu2AlH (DIBAL)H3O+ OHCOROAlHHHHLi+-COROAlX3HAlHHHHLi+-CHOAlX3HCOHH HH3O+CORO AliBuH iBu COROAlX3HAliBuH iBu H3O+COHLAHDIBAL
  58. 58. HBR2BR2HHBR2iBu2AlHAliBu2HI2I
  59. 59. AlCH3H3CH3COROR+ MeMgBrROMgBrMeOROR+ Me3AlROAlX2MeROHMeH3O+
  60. 60. TiCl4 + Et3AlTi ClEt3Al- Et2AlClTi EtH2C CH2Ti CH2H2C EtH2C CH2TiEt
  61. 61. :25.8SiO2Si
  62. 62. 131 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18H HeLi Be B C N O F NeNa Mg Al Si P S Cl ArK Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br KrRb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I XeCs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At RnFr Ra Ac
  63. 63. CH4: -164CO2:-78.5SiO2SiH4: -112
  64. 64. Si CCH3SiH3C CH3CH3tetramethylsilaneEtSiEtHEttriethylsilaneEtSiEtClEtOSiEtEtEtchlorotriethylsilaneOSiMeMeMeSiMeMeMe
  65. 65. 1s2s3s1s2s3s2sp33sp3CSi2px 2py 2pz3px 3py 3pz3px 3py 3pz2px 2py 2pz
  66. 66. 3sp32sLi C SiLi C C Siδ+ δ- δ- δ+CSi2sp3
  67. 67. • • •  250 -70• SiOSiOSiOSiORR RR RR RR
  68. 68. SiO2C- CO2 Si 99 SiCl4Cl2H3C ClCuSiCH3CH3ClCl
  69. 69. SiOSiOSiOSiORR RR RR RRSiOSi:SiCH3CH3ClCl SiCH3CH3OHHOHOSiOSiRR RROH+2 H2O- 2 HCl- H2OSiOSiOSiOSiORR RR RR RRR = CH3
  70. 70. C C C Si Si Si1.54 Å 1.90 Å 2.34 Å1.5
  71. 71. ●●SiOSiOSiOSiORR RR RR RRC Si
  72. 72. C O Si O81 kcal/mol 114 kcal/molC F108 kcal/molSi F160 kcal/molSi O Si F
  73. 73. OHOOOMgBrOHOH3COHO CH3MgBrOOMgBrMgBrCH3–MgBr+ CH3–HOHOOOSiEt3Et3Si-ClEt3NCH3MgBrOOHSiEt3H3CH3O++ E NH+Cl-
  74. 74. Si ClEt3SiCltBuMe2SiClMe3SiClOOHSiR3H3CBu4N+F-(TBAF)OOHSiH3CEtEtEtF-OHOHH3CH2O+ Et3SiF
  75. 75. •  1.•  2. β•  3. α
  76. 76. 1.C SiC Cδ+δ−CCH3H3CCH3CH31H NMR0.9 ppmSiCH3H3CCH3CH30.0 ppm
  77. 77. 2. βSiR3+HROSiR3+HRO TiCl4SiR3+HROCl4TiSiR3HROCl4Ti-+αβSiR3+HROCl4Ti-αβ ROHH2OTiCl4
  78. 78. βSiR3HROCl4Ti+βp+-2sp3 2sp3 2sp33sp3SiCCCC-Si σpC-Si σp
  79. 79. 3. αR Bu Li+R3Si Bu Li+ R3SiBuLiR3SiBuLiαα
  80. 80. C C Si SiC C Si SiC C Si Si2004(A. Sekiguchi)1981(R. West)
  81. 81. (Sekiguchi et al., 2004)1.20 Å 2.06 Å180° 137.4°C C Si Si
  82. 82. BuSnOSnBuBu BuBuBu
  83. 83. BuSnOSnBuBu BuBuBu××
  84. 84. PbC2H5H5C2C2H5C2H51970
  85. 85. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18H HeLi Be B C N O F NeNa Mg Al Si P S Cl ArK Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br KrRb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I XeCs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At RnFr Ra Ac
  86. 86. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18H HeLi Be B C N O F NeNa Mg Al Si P S Cl ArK Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br KrRb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I XeCs Ba La Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At RnFr Ra Ac
  87. 87. d1s2s2px 2py 2pz3s3px 3py 3pz4s3d4px 4py 4pzxyzdxz dyzdx2-y2 dxydz2
  88. 88. 2s2px 2py 2pzC CCsp3 sp2sp2px 2py 2pz2s4s3d4px 4py 4pzxyzdxz dyzdx2-y2dxydz24s4px 4py 4pzM MM M
  89. 89. 4s3d4px 4py 4pzxyzdxz dyzdx2-y2dxydz24s4px 4py 4pzM MM MTrigonal bipyramiddsp3
  90. 90. C C C CM O M O
  91. 91. N PR2C CR2RC CRC OIrPh3PClCOPPh3PtClClClCH2CH2-K+VaskaZeise
  92. 92. CCR RRRMCCR RRRMMM
  93. 93. R MgX + FeCl2complex mixture ???MgBr+ FeCl2Fe(HF/LANL2DZ)
  94. 94. •  →R2C CR2Ph3PRhCl PPh3PPh3WilkinsonH2R2C CR2H H
  95. 95. R2C CR2Ph3PRhICl PPh3PPh3WilkinsonPh3PRhICl PPh3S Ph3PRhIIICl PPh3SHHPh3PRhIIICl PPh3HHR2C CR2Ph3PRhIIICl PPh3SHC CHR2C CR2H HH H
  96. 96. Ph3PRhICl PPh3S Ph3PRhIIICl PPh3SHHHHPh3PRhICl PPh3SH H14 16Mg0R BrMgIIR Br
  97. 97. MgIIRBrPh3PRhIIICl PPh3HHR2C CR2Ph3PRhIIICl PPh3SHC CHCR2OMgIIBr OCR
  98. 98. Ph3PRhIIICl PPh3SHC CHPh3PRhICl PPh3SR2C CR2H H16 14
  99. 99. d1s2s2px 2py 2pz3s3px 3py 3pz4s3d4px 4py 4pzxyzdxz dyzdx2-y2 dxydz2
  100. 100. C C C CM O M O
  101. 101. CCR RRRMCCR RRRMMM
  102. 102. 2s2px 2py 2pzC CCsp3 sp2sp2px 2py 2pz2s4s3d4px 4py 4pzxyzdxz dyzdx2-y2dxydz24s4px 4py 4pzM MM M
  103. 103. 4s3d4px 4py 4pzxyzdxz dyzdx2-y2dxydz24s4px 4py 4pzM MM MTrigonal bipyramiddsp3
  104. 104. 18182s2px 2py 2pzHCHHHsp3C O4s3d4px 4py 4pzLMLLLLXMLMLLLLL
  105. 105. LMLLLLLLMLL LLH2C CH2●18●18
  106. 106. P3PRhClPPh3P3PP3PCl - -12e-2e-0RhP3PRhClPPh3P3PWilkinson
  107. 107. 202e-Cr0Cr(CO)6 O CPtClClClCH2CH2-K+ZeiseCl - -32e-2e- 0PtH2C CH2
  108. 108. 3-26e-FeFe+ FeCl22 FeFe2e-Fe4e-Fe6e-Fe6e-
  109. 109. 4: π--24e-Ni+ NiCl224e-MgBr NiMMMMM2e- 4e-Ni
  110. 110. •  →R2C CR2Ph3PRhCl PPh3PPh3WilkinsonH2R2C CR2H H
  111. 111. R2C CR2Ph3PRhICl PPh3PPh3WilkinsonPh3PRhICl PPh3S Ph3PRhIIICl PPh3SHHPh3PRhIIICl PPh3HHR2C CR2Ph3PRhIIICl PPh3SHC CHR2C CR2H HH H
  112. 112. Ph3PRhICl PPh3PPh3 WilkinsonPh3PRhICl PPh3S- PPh3 + S (Solvent)16e-16e-
  113. 113. Ph3PRhICl PPh3S Ph3PRhIIICl PPh3SHHHHPh3PRhICl PPh3SH H16e- 18e-Mg0R BrMgIIR Br
  114. 114. MgIIRBrPh3PRhIIICl PPh3HHR2C CR2Ph3PRhIIICl PPh3SHC CHCR2OMgIIBr OCR
  115. 115. Ph3PRhIIICl PPh3SHC CHPh3PRhICl PPh3SR2C CR2H H18 16
  116. 116. X + NuPd(0) catalyst- X-NuX = –OAc–X–OCO2RRO OROO/ baseR NH2R OHOAc +MeO OMeOO Pd(PPh3)4 catalystNaHCO2MeCO2Me
  117. 117. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18H HeLi Be B C N O F NeNa Mg Al Si P S Cl ArK Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br KrRb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I XeCs Ba La Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At RnFr Ra AcPd:10 , 1 g ¥1200 (cf. 1 g, ¥2300)
  118. 118.     
  119. 119. 1.M XR1 R2+Pd catalystR1 R2– MXMgBrR1BrR2+Pd(PPh3)4Kumada-Tamao couplingCross-couplingR1 R2– MgBr2B(OH)2R1BrR2+Pd(PPh3)4Suzuki-Miyaura couplingR1 R2– BX3NaOH
  120. 120. Tetrakis(triphenylphosphine)palladium(0)Pd(PPh3)4PPh3PdPh3PPPh3PPh3Pd0: d1018 e–Pd(PPh3)4 Pd(PPh3)3 Pd(PPh3)2 Pd(PPh3) Pd– PPh3 – PPh3 – PPh3 – PPh3+ PPh3 + PPh3 + PPh3 + PPh318 e– 16 e– 14 e– 12 e–
  121. 121. Pd(PPh3)4 Pd(PPh3)3 Pd(PPh3)2 Pd(PPh3)– PPh3 – PPh3 – PPh3+ PPh3 + PPh3 + PPh318 e– 16 e– 14 e– 12 e–Pd0Ph3PPh3PPdIIArPh3PPh3PBr– Br14 e–16 e–Pd0: d10 PdII: d8Pd
  122. 122. PdIIArPh3PPh3PBr+ Ar – MBr – MPdIIArPh3PPh3PArPdI : d8, 16e- PdI : d8, 16e-BOHOHBOHOHOH-OH-
  123. 123. PdIIArPh3PPh3PBr+ Ar – MBr – MPdIIArPh3PPh3PArPdII: d8, 16e- PdII: d8, 16e-Pd0Ph3PPh3PAr Ar+Pd0: d10, 14e-
  124. 124. M XR1 R2+Pd catalystR1 R2– MXMR MXX RSnBu3 SiR3ZnXStille Coupling Negishi Coupling Hiyama CouplingF–
  125. 125. Mizoroki-HeckXR2Pd catalyst+R1R1R2 + HNR3R3N
  126. 126. LnPd0PdIIArLLBr– BrPdIIArLBrRR+– LPdIIArLBrRPdIIL BrRAr
  127. 127. βPdIIL BrRArHPdIIL BrRHArArR+LnPdIIBrHLnPdIIBrHLnPd0 + HBr
  128. 128. Mizoroki-HeckXR2Pd catalyst+R1R1R2 + HNR3R3N
  129. 129. LnPd0PdIIArLLBr– BrPdIIArLBrRR+– LPdIIArLBrRPdIIL BrRAr
  130. 130. βPdIIL BrRArHPdIIL BrRHArArR+LnPdIIBrHLnPdIIBrHLnPd0 + HBr
  131. 131. 4: π--24e-Ni+ NiCl224e-MgBr NiMMMMM2e- 4e-Ni
  132. 132. X + NuPd(0) catalyst- X-NuX = –OAc–X–OCO2RRO OROO/ baseR NH2R OHOAc +MeO OMeOO Pd(PPh3)4 catalystNaHCO2MeCO2Me
  133. 133. SOCO2MeNO NH2Ph CO2MePd catalystSNONHPhCO2Me+ CO2 + MeOHSHNONHCOOH(+)-biotin
  134. 134. OAc LnPd(0)+Pd(0)OAcOAcHH HHPd(II)HHPd(II)+LAcOPd(0)AcO-σ (η1)π- (η3)Pd
  135. 135. PdMeO OMeOOHHPd(II)LAcO+ NaHMeO OMeOOH HHNa–+MeO OMeOOHNaOMeMeOO OHNaMeO OMeOOHNaHHPd(II)LAcOHHCO2MeCO2MePd(0)+ AcO–H H–OAcHHHHCO2MeCO2Me2(retention)
  136. 136. C OOOCCpx py pzssppx pyO OspC CCC CsppypxspCOCOCHOMOLUMO
  137. 137. LUMOC OC O HOMOC OMC OMback donationdonation
  138. 138. •  →R2C CR2Ph3PRhCl PPh3PPh3WilkinsonH2R2C CR2H H
  139. 139. R2C CR2Ph3PRhICl PPh3PPh3WilkinsonPh3PRhICl PPh3S Ph3PRhIIICl PPh3SHHPh3PRhIIICl PPh3HHR2C CR2Ph3PRhIIICl PPh3SHC CHR2C CR2H HH H
  140. 140. Ph3PRhICl PPh3PPh3 WilkinsonPh3PRhICl PPh3S- PPh3 + S (Solvent)16e-16e-
  141. 141. Ph3PRhICl PPh3S Ph3PRhIIICl PPh3SHHHHPh3PRhICl PPh3SH H16e- 18e-Mg0R BrMgIIR Br
  142. 142. MgIIRBrPh3PRhIIICl PPh3HHR2C CR2Ph3PRhIIICl PPh3SHC CHCR2OMgIIBr OCR
  143. 143. Ph3PRhIIICl PPh3SHC CHPh3PRhICl PPh3SR2C CR2H H18 16
  144. 144. X + NuPd(0) catalyst- X-NuX = –OAc–X–OCO2RRO OROO/ baseR NH2R OHOAc +MeO OMeOO Pd(PPh3)4 catalystNaHCO2MeCO2Me
  145. 145. C OOOCCpx py pzssppx pyO OspC CCC CsppypxspCOCOCHOMOLUMO
  146. 146. LUMOC OC O HOMOC OMC OMback donationdonation
  147. 147. •  →R2C CR2Ph3PRhCl PPh3PPh3WilkinsonH2R2C CR2H H
  148. 148. R2C CR2Ph3PRhICl PPh3PPh3WilkinsonPh3PRhICl PPh3S Ph3PRhIIICl PPh3SHHPh3PRhIIICl PPh3HHR2C CR2Ph3PRhIIICl PPh3SHC CHR2C CR2H HH H
  149. 149. Ph3PRhICl PPh3PPh3 WilkinsonPh3PRhICl PPh3S- PPh3 + S (Solvent)16e-16e-
  150. 150. Ph3PRhICl PPh3S Ph3PRhIIICl PPh3SHHHHPh3PRhICl PPh3SH H16e- 18e-Mg0R BrMgIIR Br
  151. 151. MgIIRBrPh3PRhIIICl PPh3HHR2C CR2Ph3PRhIIICl PPh3SHC CHCR2OMgIIBr OCR
  152. 152. Ph3PRhIIICl PPh3SHC CHPh3PRhICl PPh3SR2C CR2H H18 16
  153. 153. R2C CR2Ph3PRhICl PPh3S Ph3PRhIIICl PPh3SHHPh3PRhIIICl PPh3HHR2C CR2Ph3PRhIIICl PPh3SHC CHR2C CR2H HH H→R2C CR2+ H2R2C CR2+ H2+ Rh cat.
  154. 154. 91○
  155. 155. L-DOPACOOHNH2HOHOL-DOPACOOHNH2HOHOCOOHNHCOCH3MeOHOCOOHNH2HOHOL-DOPA D-DOPAL-DOPA -DOPA.
  156. 156. COOHNHRMeOHOCOOHNHRMeOHOCOOHNHCOCH3MeOHOL-DOPA D-DOPACOOHNH2HOHOCOOHNHCOCH3MeOHOCOOHNH2HOHOL-DOPA D-DOPA
  157. 157. W. S. Knowles1972,L-DOPACOOHNH2HOHOCOOHNHCOCH3MeOHOL-DOPAP POMeMeO(R,R)-DIPAMP
  158. 158. DIOPPRhIIIClPHHPPh2PPh2OOCOOHNHCOCH3MeOHOCOOHNHCOCH3MeOHODIOPCOOHNHCOCH3MeOHOPRhIIIClPHHPRhIIIClPHHSPP=
  159. 159. PRhIIIClPHHCOOHNHCOCH3MeOHOCOOHNHCOCH3MeOHOPRhIIIClPHHCOOHRHNMeOHOCOOHNHRMeOHOL-DOPA D-DOPAPRhIIIClPHHHPRhIIIClPH
  160. 160. BINAPPPh2PPh2OO(R, R)-DIOPPPh2PPh2(S)-BINAPKagan Noyori
  161. 161. R + H2 + CORCHORCHO +RhCo etc...Ph3P RhPPh3PPh3HCO+trigonal bipyramid(P3P)3RhH(CO)Ph3PRhIIICl PPh3SHH(Ph3P)3RhClH2, -PPh3cf.
  162. 162. 1Ph3P RhIPPh3PPh3HCOPh3PRhIPPh3HCO– PPh3+ PPh318e 16ePh3P RhIPPh3HCOR18eR Ph3PRhIPPh3H2CCOCH2R16e
  163. 163. 2Ph3PRhIPPh3H2CCOCH2R16ePh3PRhIPPh3H2CCOCH2RCO18eCOPh3PRhIPPh3COCORRhIH2CCH2RCORhICOR16e
  164. 164. 3H2Ph3PRhIPPh3COCOR16ePh3PRhIIICOHPPh3HCOR18ePh3PRhIPPh3HCORCHO+
  165. 165. linear or branchPh3P RhIPPh3HCOR18ePh3PRhIPPh3CO16eRCHOlinear18ePh3P RhIPPh3HCORPh3PRhIPPh3COR16eRCHObranchRHH
  166. 166. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18H HeLi Be B C N O F NeNa Mg Al Si P S Cl ArK Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br KrRb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I XeCs Ba La Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At RnFr Ra AcCu:11 , 1 g ¥0.9 (cf. 1 g, ¥2,300, 1 g, ¥0.025)
  167. 167. (I)R Li + CuXX = Cl, Br, IR CuR Li + CuX R Cu2 R Li+–(Gilman
  168. 168. 1,4-O+ RLiR OLi R OLi+hydrolysis hydrolysisR OH R O1,2-major1,4-minorO+ R2CuLiR OMhydrolysisR O1,4-
  169. 169. HSABR LiR2CuLiCCCO
  170. 170. R2CuLi +O OCu(I)RRLi OCu(III)RRLiOLiR+ RCu1,4-R2CuLiR CuLiRLiR RCuCCCu3d
  171. 171. (I) 2R XR2CuLi + R R–RCu–LiXR XRMgBrR RRLiRCHO R ROMR ROHR XX = Cl, Br, I ....R M + R RMgBr X+Pd(PPh3)4R X
  172. 172. C XR2R3R1R2CuLi + CR2CuIIIR2R3R1– LiXCR2R3R1R– RCu
  173. 173. 1,2- ..OR OM R OM+R2CuLiR OMRLi, RMgBr 1,2 - 1,4-1,4-RLi / CeCl3orRMgBr/ CeCl3R OM1,2 -
  174. 174. (Ce)1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18H HeLi Be B C N O F NeNa Mg Al Si P S Cl ArK Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br KrRb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I XeCs Ba Ln Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At RnFr Ra Ac2Ce2O3:1 g ¥3.0La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
  175. 175. CeCl3•nH2O CeCl3HFR LiRCeCl2 •LiCl(RCeCl2 •LiCl +OHydrolysisOCeRCeCl2CeIII :OCeCl2ROHR
  176. 176. 2OH HRLi OH HRLiOLiRCeCl2OCeCl2RONaBH4 / CeCl3MeOHOHHLuche
  177. 177. Li+, Mg2+, Fe3+, Ni2+R3P, CO, H-, R-,Pd2+, Pd0, Ni0, Rh1+R3N, RO-, F-C CHH HH
  178. 178. (cone angle)PMθPMPPH3C CH3PCH3θ182°145°118°
  179. 179. Tetrakis(triphenylphosphine)palladium(0)Pd(PPh3)4PPh3PdPh3PPPh3PPh3Pd0: d1018 e–Pd(PPh3)4 Pd(PPh3)3 Pd(PPh3)2 Pd(PPh3) Pd– PPh3 – PPh3 – PPh3 – PPh3+ PPh3 + PPh3 + PPh3 + PPh318 e– 16 e– 14 e– 12 e–
  180. 180. Pd(PPh3)4 Pd(PPh3)3 Pd(PPh3)2 Pd(PPh3)– PPh3 – PPh3 – PPh3+ PPh3 + PPh3 + PPh318 e– 16 e– 14 e– 12 e–Pd0Ph3PPh3PPdIIArPh3PPh3PBr– Br14 e–16 e–Pd0: d10 PdII: d8Pd
  181. 181. PdPd(PPh3)4 18 →Pd(PPh3)2 14 →Pd(PtBu3)2 14●
  182. 182. B(OH)2IR1R2+R1 R2Pd(PPh3)4baseBrR2ClR2orB(OH)2R1+ R1 R2ClR2B(OH)2R1+ R1 R2Pd(PtBu3)2base
  183. 183. MLLLLMLLLLLMLLLLLMLLLLLMLLLLLMLLL- L=k[complex][L], SN2i =k[complex], SN1trigonal bipyramid
  184. 184. R2C CR2Ph3PRhICl PPh3PPh3WilkinsonPh3PRhICl PPh3S Ph3PRhIIICl PPh3SHHPh3PRhIIICl PPh3HHR2C CR2Ph3PRhIIICl PPh3SHC CHR2C CR2H HH H
  185. 185. MLL LLML LL+ LL = CO, C2H4 > PR3, H- > R- > X- > NR3 > H2O
  186. 186. MPh2P PPh2MPPh3 M PPh3+MPh2P PPh2+Ph2P PPh2M(bite angle)Ph2P PPh2PPh2Ph2PPh2P PPh2dppedpppdppbdppp1,3-bis(diphenylphosphino)propaneFePPh2PPh2dppf(bite angle)
  187. 187. PtClCl PEt3Et3PPtEt3P ClEt3PL = R- > PR3, > CO > NR3 > X-Cl2.25 Å 2.42 Å2.31 Å 2.32 Å

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