SLIDE 1
Rh Cl Cl
2
: 5 - Rh - - PowerPoint PPT Presentation
: 5 - Rh - - PowerPoint PPT Presentation
1L2-51 ( : 5 - Rh CATALYTIC
SLIDE 2
SLIDE 3
Rh H Cl NH3 –NH3 +NH3 possible active catalyst Rh NH3
DESIGN OF Rh TETHERED COMPLEX
Rh H Cl This work R, R' = H, CH3 Rh Cl H
N
Rh Cl H
N R R' R R'
SLIDE 4
Rh
- range powder
R, R' = H, CH3 Cl Cl Cl Rh Cl NRR'•HCl R'RN HCl• Hessen, B. Organometallics, 2000, 19, 4084. NRR' 1) HCO2C2H5 2) LiAlH4 NRR' HCl in (C2H5)2O CH3OH 50 °C, 2 h NRR' R, R' = H, CH3 CH3OH reflux, 72 h RhCl3•3H2O CH2Cl2, rt, 9 h (CH3)3COK (1 equiv/Rh)
- range powder
Rh Cl Cl N R R'
SYNTHESIS OF C2 TETHERED COMPLEXES
R, R' = H R = H, R' = CH3 R, R' = CH3 36% yield 27% yield 23% yield + two isomers
- HCl
3.89 (m, 2H, CH2NHCH3) 3.58 (br, 1H, NH) 2.54 (d, 3H, 3J = 6.1 Hz, NHCH3) 2.36 –2.45 (m, 2H, CH2CH2NHCH3) 1.89, 1.86, 1.71, 1.67 (s, 3H each, CH3)
1H NMR (δ, CDCl3) 13C NMR (δ, CDCl3)
106.2 (d, 2JRhC = 8.8 Hz, C5(CH3)4) 99.3, 95.9, 87.6, 84.5 (C5(CH3)4) 66.6, 39.3, 23.5, 9.3, 8.7 R = H, R' = CH3
SLIDE 5
Li + two isomers 1) 2) H2O THF －78 °C → rt, 3 h CH3OH 50 °C, 4 h HCl in (C2H5)2O (1 equiv) Boc = CO2C(CH3)3
SYNTHESIS OF C3 TETHERED COMPLEX
CH3OH reflux, 12 h CH2Cl2, rt, 9 h (CH3)3COK (1 equiv) Rh Cl Cl N H2 37% yield
- range powder
NBoc O Br Li 0 °C, 4 h (C2H5)2O OH NHBoc NH3Cl 3.30 (br, 2H, (CH2)2CH2NH2)
1H NMR (δ, CDCl3)
98.7 (d, 2JRhC = 7.6 Hz, C5(CH3)4) 96.4 (d, 2JRhC = 8.4 Hz, C5(CH3)4) 86.4 (d, 2JRhC = 9.5 Hz, C5(CH3)4) 39.5, 30.3, 18.9, 9.1, 8.5
13C NMR (δ, CD2Cl2)
1.80, 1.66 (s, 6H each, C5CH3) 2.68 (br, 2H, NH2) 2.14 –2.10 (m, 2H, CH2(CH2)2NH2) 2.03 (br, 2H, CH2CH2CH2NH2) RhCl3•3H2O
SLIDE 6
Rh Cl Cl N H2 NHTf NHTf THF, reflux, 9 h (CH3)3COK (2 equiv) Rh TfN NTf N H2 + n = 0, 1
- range crystals
Tf = CF3SO2
MOLECULAR STRUCTURES OF C2 AND C3 TETHERED DERIVATIVES
n n n = 0, 1 P21/a (#14) R1 = 0.033 wR2 = 0.120 P21/n (#14) R1 = 0.034 wR2 = 0.130
SLIDE 7
Rh Cl Cl N H2 1) AgSbF6 2) P(C6H5)3 Rh (C6H5)3P Cl N H2 SbF6
SYNTHESIS OF CATIONIC TETHERED COMPLEXES
- range powders
n = 0 33% yield n = 1 45% yield
1H NMR (δ, CD2Cl2)
7.46 –7.58 (m, 15H, C6H5) 2.73 (br, 2H) 2.61 (br, 1H) 2.05 –2.35 (m, 5H) 1.83 (d, 3H, 4JHP = 6.8 Hz, CH3) 1.74 (s, 3H, CH3) 1.08 (s, 3H, CH3) 0.97 (d, 3H, 4JHP = 5.9 Hz, CH3)
31P NMR (δ, CD2Cl2)
34.8 (d, 1JPRh = 141.6 Hz)
1H NMR (δ, CD2Cl2)
7.43 –7.58 (m, 15H, C6H5) 3.94 (m, 1H) 3.77 (m, 2H) 2.67 (m, 2H) 2.20 –2.28 (m, 1H) 2.13 (d, 3H, 4JHP = 7.6 Hz, CH3) 1.69 (s, 3H, CH3) 1.21 (s, 3H, CH3) 0.97 (d, 3H, 4JHP = 5.4 Hz, CH3)
31P NMR (δ, CD2Cl2)
33.1 (d, 1JPRh = 141.0 Hz) n n n = 0, 1 n = 0 n = 1 THF, rt
SLIDE 8
Rh cat + CH3OH 70 °C, 2 h amine:alcohol cat. O
- HCO2H
N + 54:46 R, R' = H R = H, R' = CH3 R, R' = CH3 96:4 dimer 58 68 88:12 70 68 63 65:35 83:17 determined by NMR 1 equiv
CATALYTIC REACTION
substrate/[Rh] = 100 0.1 M in CH3OH Rh Cl Cl
2
dimer Rh Cl Cl N R R' R, R' = H, CH3 Reductive amination of benzaldehyde OH Rh Cl Cl N H2 H TON C2 C2 C2 C3 C3 C2 HN C6H5 C6H5 C6H5 C6H5
SLIDE 9
R = H, CH3 Synthesis of Rh tethered complexes Rh Cl Cl N H2
SUMMARY
Rh Cl Cl N R CH3 C6H5 R1 Rh cat + CH3OH 70 °C, 2 h O ・ HCO2H HN C6H5 N R3 R2 + C6H5 R1 R1 OH 1 equiv substrate/[Rh] = 100 0.1 M in CH3OH R1 = H, R2, R3 = CH2C6H5 amine : alcohol = up to 96 : 4 Reductive amination R3 R2 Rh Ph3P Cl N H2 SbF6 n Rh TfN NTf N H2 n = 0, 1 n
SLIDE 10
Rh N Rh N C0 C0 θ θ Rh – C0(Å) θ(°) C2 C3 2.094(5) 2.147(4) 93.8(2) 81.7(2)
STRUCTURE OF TETHER RINGS
Rh – N(Å) 2.139(4) 2.114(4) C2 C3
SLIDE 11
C6H5 R1 Rh cat + CH3OH 70 °C, 2 h O ・ HCO2H HN C6H5 N R3 R2 + C6H5 R1 R1 OH 1 equiv substrate/[Rh] = 100 0.1 M in CH3OH R3 R2 Sbstrate scope 93:7 43 CH3 98:2 99 H
- (CH2)4-
90:10 14
- (CH2)4-