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Design and synthesis of imidazolium salt derived from (L)-Valine.
Investigation of their potential in Chiral Molecular Recognition.
Hervé Clavier, Loïse Boulanger, Nicolas Audic, Loïc Toupet, Marc Mauduit* and JeanClaude Guillemin*
H. Clavier, L. Boulanger, N. Audic, Dr. M. Mauduit, Dr. J.C. Guillemin
UMR CNRS 6052, Ecole Nationale Supérieure de Chimie, Institut de Chimie de Rennes,
35700 Rennes (France)
Fax : 33 (0)2 23 23 81 08
E-mail : marc.mauduit@ensc-rennes.fr
L. Toupet, UMR CNRS 6626, Université de Rennes 1, 35700 Rennes (France)
General. 1H (400 MHz), 13C (100 MHz), 31P (162 MHz) and 19F (376.5 MHz) NMR spectra
were recorded on a Bruker ARX400 spectrometer with complete proton decoupling for
nucleus other than 1H. Chemical shifts are reported in ppm from tetramethylsilane with the
solvent resonance as the internal standard (CDCl3, 1H:  7.27 ppm, 13C: 77.0 ppm, CD2Cl2,
1
H: 5.31 ppm, 13C: 53.7 ppm and (CD3)2CO: 1H: 2.05 ppm, 13C: 205.1 ppm). Data are
reported as follows: chemical shift ( in ppm, multiplicity (s = singlet, d = doublet, t = triplet,
q = quadruplet, sept = septuplet, hept = heptuplet, bd = broad, m = multiplet), coupling
constants (Hz), integration and attribution. High-resolution mass spectra (HRMS) were
recorded at the Centre Régional de Mesures Physiques de l’Ouest (CRMPO), Université de
Rennes 1 on a Micromass ZABSpecTOF instrument. Melting points were measured on a
heating microscope Reichert and were uncorrected. Optical rotations were recorded using a
polarimeter Perkin-Elmer 341.
Materials. All non-aqueous reactions were performed under an argon atmosphere using ovendried glassware. Toluene was distilled from sodium metal under nitrogen. Tetrahydrofuran
and diethyl ether were distilled from sodium metal/benzophenone ketyl under nitrogen.
Dichloromethane, methanol and N-methylmorpholine were distilled from calcium hydride
1
Supplementary Material (ESI) for Chemical Communications
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under nitrogen. The 2N anhydrous HCl/solution was prepared by addition, at 0°C, of acetyl
chloride to dry methanol. All others chemical reagents and solvents were obtained from
commercial sources and used without further purification. Analytical TLC were performed on
Merck silica gel 60F254 plates, and visualized under UV-light. Chromatographic purifications
were performed on a column with 230-400 mesh silica gel (Merck 9385) using the indicated
solvent system.
[1-(2-tert-Butyl-phenylcarbamoyl)-2-methyl-propyl]-carbamic acid tert-butyl ester :
To a solution of BOC-L-Valine 1 (2.37 g, 10 mmol) in dry THF (50 mL) was added Nmethylmorpholine (1.16 mL, 10.5 mmol, 1.05 equiv.). The mixture was cooled to -15°C then
isobutyl chloroformate (1.37 mL, 10.5 mmol, 1.05 equiv.) was added dropwise. After 30 min
stirring, 2-tert-butylaniline (1.64 mL, 10.5 mmol, 1.05 equiv.) was added, and the resulting
solution was stirred for 48h at room temperature. After evaporation of the solvent, the residue
was dissolved in AcOEt and washed successively with saturated NaHCO3 solution, 0.1N HCl
solution and brine. The organic layer was dried over MgSO4, filtered and concentrated in
vacuo. The resulting solid was purified by washing with cold pentane to afford the amide as a
white solid (2.76 g, 79 %).
Mp = 143°C (pentane).
[]D20 = -49.2 (c = 1 in chloroform).
1H
NMR (400 MHz, CDCl3): = 7.98 (s, 1H, ArNH), 7.67-7.14 (m, 4H, 4CHar), 5.02 (bd s,
1H, NH) 4.14 (dd, J(H,H) = 5 and 9 Hz, 1H, 1CH), 2.47 (m, 1H, 1CH), 1.47 (s, 9H, 3CH3),
1.41 (s, 9H, 3CH3), 1.07 (d, J(H,H) = 7 Hz, 3H, CH3), 0.99 (d, J(H,H) = 7 Hz, 3H, CH3).
13C
NMR (100 MHz, CDCl3): = 170.0, 155.9, 134.93 (2C), 126.8, 126.5 (2C), 126.0, 80.4,
60.9, 34.4, 30.6 (3C), 29.9, 28.3 (3C), 19.6 (2C).
HRMS (EI, M+), calcd for C20H32N2O3: 348.2412, found: 348.2413.
N1-(2-tert-Butyl-phenyl)-3-methyl-butane-1,2-diamine (2):
To a solution of amide (3.48 g, 10 mmol) in dry methanol (40 mL) was added dropwise a 2N
anhydrous HCl/methanol solution (50 mL, 100 mmol, 10 equiv.) at 0°C. The mixture was
warmed to room temperature and stirred overnight. After evaporation of the solvent, the
resulting salt was dissolved in water and treated by 1N NaOH solution to reach a basic pH.
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The aqueous layer was saturated with sodium chloride and extracted with dichloromethane.
The combined organic layers were dried over MgSO4 and concentrated in vacuo to afford the
corresponding free amine as an anamorphous solid which was directly dissolved in dry THF
and slowly added to a suspension of LiAlH4 (2.28 g, 60 mmol, 6 equiv.) in dry THF at 0°C.
The resulting mixture was heated to reflux and stirred for 48h. After cooling to 0°C, water and
15% NaOH solution were added dropwise and the resulting solid material was removed by
filtration. The filtrate was concentrated in vacuo and the residue was purified by flash
chromatography (CH2Cl2/methanol 95/5) to afford the diamine 2 as yellow oil (1.8 g, 78%,
two steps).
[]D20 = +12.8 (c = 1 in chloroform).
1H
NMR (400 MHz, CDCl3): = 7.28 (dd, J(H,H) = 1.5 and 8 Hz, 1H, 1CHar), 7.16 (dt,
J(H,H) = 1.5 and 8 Hz, 1H, 1CHar), 6.82 (m, 2H, 2CHar), 4.73 (bd s, 1H, NH), 3.32 (d, J(H,H)
= 10 Hz, 1H, 1CH), 2.99 (m, 2H, 1CH2), 1.74 (hept, J(H,H) = 7 Hz, 1H, 1CH), 1.48 (s, 9H,
3CH3), 1.19 (bd s, 2H, NH2), 1.03 (d, J(H,H) = 7 Hz, 3H, CH3), 1.01 (d, J(H,H) = 7 Hz, 3H,
CH3).
13C
NMR (100 MHz, CDCl3): = 146.9, 133.4, 127.0, 126.1, 116.6, 111.5, 56.3, 48.2, 34.2,
32.9, 29.8 (3C), 19.4, 18.0.
HRMS (EI, M+), calcd for C15H26N2: 234.2096, found: 234.2098.
1-(2-tert-Butyl-phenyl)-4-isopropyl-4,5-dihydro-1H-imidazole (3):
To a solution of diamine 2 (5 mmol) in dry diethyl ether (25 mL) was added dropwise, at 0°C,
a 2N anhydrous HCl/methanol solution (2.5 mL, 5mmol, 1 equiv.). A white precipitate was
immediately formed. After 10 min. stirring, the solvent was evaporated to afford the
corresponding chlorhydrate of diamine in quantitative yield. The salt was dissolved in dry
toluene (15 mL) , trimethylorthoformate (2.75 ml, 25 mmol, 5 equiv.) was added and the
mixture was heated to 90°C for 12h. After cooling to room temperature, dichloromethane
(100 mL) and 1N NaOH aq. solution (60mL) were added. The organic layer was washed with
brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by flash
chromatography (CH2Cl2/methanol 95/5) to afford the imidazole 3 as colorless needles (1.05
g, 86%, two steps).
Mp = 43-45°C (AcOEt).
[]D20 = -12.6 (c = 1 in chloroform).
3
Supplementary Material (ESI) for Chemical Communications
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NMR (400 MHz, CDCl3): = 7.46-7.43 (m, 1H, 1CHar), 7.26-7.22 (m, 2H, 2CHar), 7.04-
1H
7.02 (m, 1H, 1CHar), 6.81 (d, J(H,H) = 2 Hz, 1H, 1CH), 3.94 (dt, J(H,H) = 2 and 10 Hz, 1H,
1CH), 3.68 (t, J(H,H) = 10 Hz, 1H, 1CH), 3.19 (t, J(H,H) = 10 Hz, 1H, 1CH), 1.87 (hept,
J(H,H) = 7 Hz, 1H, 1CH), 1.41 (s, 9H, 3CH3), 1.10 (d, J(H,H) = 7 Hz, 3H, CH3), 0.97 (d,
J(H,H) = 7 Hz, 3H, CH3).
13C
NMR (100 MHz, CDCl3): = 156.8, 149.1, 141.9, 129.6, 127.8, 127.5, 127.3, 73.2, 58.2,
35.4, 33.1, 31.3 (3C), 19.5, 18.8.
HRMS (EI, M+), calcd for C16H24N2: 244.1939, found: 244.1923
3-(2-tert-Butyl-phenyl)-5-isopropyl-1-methyl-d3-4,5-dihydro-3H-imidazol-1-ium
hexafluoro phosphate (4a):
Imidazole 3 (1.2 g, 5 mmol) was dissolved in acetone (5 mL) and iodomethane (375 L, 6
mmol, 1.2 equiv.) was added and the reaction mixture was stirred at room temperature for 2h.
The reaction mixture was concentrated to dryness and the white residue dissolved in dry
acetone. KPF6 (1.1 g, 6 mmol, 1.2 equiv.) was added at room temperature. After 30 min.
stirring, the solvent was evaporated under reduced pressure; the residue was dissolved in
dichloromethane and washed with brine. The organic layer was dried over MgSO4 and
concentrated in vacuo. Purification by flash chromatography (CH2Cl2/acetone 3/1) afforded
the imidazolium salt 4a as a white solid (1.91 g, 94%, two steps).
Mp = 136-138°C (AcOEt/pentane).
[]D20 = -1.6 (c = 1 in chloroform).
1H
NMR (400 MHz, CDCl3): = 7.89 (s, 1H, 1CH), 7.51 (d, J(H,H) = 8 Hz, 1H, 1CHar), 7.40
(m, 1H, 1CHar), 7.28 (m, 2H, 2CHar), 4.52 (dt, J(H,H) = 4 and 11 Hz, 1H, 1CH), 4.25 (t,
J(H,H) = 12 Hz, 1H, 1CH), 3.93 (t, J(H,H) = 11 Hz, 1H, 1CH), 3.30 (s, 3H, 1CH3), 2.38
(hept, J(H,H) = 4 Hz, 1H, 1CH), 1.38 (s, 9H, 3CH3), 1.03 (d, J(H,H) = 7 Hz, 3H, CH3), 1.00
(d, J(H,H) = 7 Hz, 3H, CH3).
13C
NMR (100 MHz, CDCl3): = 159.1, 147.3, 134.4, 130.6, 130.3, 128.7, 128.3, 67.1, 55.3,
35.7, 31.9 (3C), 26.8, 25.6, 18.0, 14.6.
19F
NMR (376.5 MHz, CDCl3): = -72.7 (d, J(F,P) = 712.8 Hz).
31P
NMR (162 MHz, CDCl3): =-143.2 (sept, J(P,F) = 712.8 Hz).
HRMS (FAB), calcd for C+: C17H24D3N2: 262.2363, found:262.2367; calcd for 2C+,PF6-:
C34H48D6F6N4P: 669.4367, found: 669.4377.
4
Supplementary Material (ESI) for Chemical Communications
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3-(2-tert-Butyl-phenyl)-5-isopropyl-1-octyl-4,5-dihydro-3H-imidazol-1-ium
hexafluoro
phosphate (4b):
Imidazole 3 (1.2 g, 5 mmol) was dissolved in acetone (5 mL) and 1-bromooctane (1.73 mL,
10 mmol, 2 equiv.) was added and the reaction mixture was stirred at reflux for 48h. KPF6
(1.1 g, 6 mmol, 1.2 equiv.) was added at room temperature. After 30 min. stirring, the solvent
was evaporated under reduced pressure; the residue was dissolved in dichloromethane and
washed with brine. The organic layer was dried over MgSO4 and concentrated in vacuo.
Purification by flash chromatography (CH2Cl2/acetone 3/1) afforded the imidazolium salt 4b
as a limpid oil (2.23 g, 70%, two steps).
[]D20 = +6.0 (c = 1.08 in chloroform).
1H
NMR (400 MHz, CDCl3): = 7.88 (s, 1H, 1CH), 7.52 (dd, J(H,H) = 1 and 8 Hz, 1H,
1CHar), 7.40 (dt, J(H,H) = 1 and 8 Hz, 1H, 1CHar), 7.29 (dt, J(H,H) = 1 and 8 Hz, 1H, 1CHar),
7.20 (d, J(H,H) = 8 Hz, 1H, 1CHar), 4.56 (dt, J(H,H) = 3 and 11 Hz, 1H, 1CH), 4.31 (t, J(H,H)
= 12 Hz, 1H, 1CH), 3.91 (t, J(H,H) = 11 Hz, 1H, 1CH), 3.76 (m, 1H, 1CH), 3.46 (m, 1H,
1CH), 2.35 (hept, J(H,H) = 3 Hz, 1H, 1CH), 1.70 (m, 2H, 1CH2), 1.38 (s, 9H, 3CH3),1.351.25 (m, 10H, 5CH2), 1.05 (d, J(H,H) = 7 Hz, 3H, CH3), 0.99 (d, J(H,H) = 7 Hz, 3H, CH3),
0.87 (m, 3H, CH3).
13C
NMR (100 MHz, CDCl3): = 158.0, 147.1, 134.0, 130.7, 130.0, 128.7, 128.3, 64.8, 54.7,
46.2, 35.7, 31.9, 31.6, 29.0, 28.8, 27.1, 26.8, 26.3, 22.5, 17.8, 14.4, 14.0.
19F
NMR (376.5 MHz, CDCl3): = -72.9 (d, J(F,P) = 712.8 Hz).
31P
NMR (162 MHz, CDCl3): = -143.2 (sept, J(P,F) = 712.8 Hz).
3-(2-tert-Butyl-phenyl)-1-(2-hydroxy-ethyl)-5-isopropyl-4,5-dihydro-3H-imidazol-1-ium
bis(trifluoromethylsulfonyl)imide (4c):
Imidazole 3 (1.2 g, 5 mmol) was dissolved in acetone (5 mL) and 2-bromoethanol (705 L,
10 mmol, 2 equiv.) was added and the reaction mixture was stirred at reflux for 48h. After
being cooled to room temperature, LiNTf2 (1.7 g, 6 mmol, 1.2 equiv.) was added at room
temperature. After 30 min. stirring, the solvent was evaporated under reduced pressure; the
residue was dissolved in dichloromethane and washed with brine. The organic layer was dried
over MgSO4 and concentrated in vacuo. Purification by flash chromatography
5
Supplementary Material (ESI) for Chemical Communications
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(CH2Cl2/acetone 3/1) afforded the imidazolium salt 4c as a yellow oil (1.75 g, 62%, two
steps).
[]D20 = +16.8 (c = 1 in chloroform).
1H
NMR (400 MHz, CDCl3): = 8.08 (s, 1H, 1CH), 7.55 (dd, J(H,H) = 1 and 7 Hz, 1H,
1CHar), 7.43 (dt, J(H,H) = 1 and 7 Hz, 1H, 1CHar), 7.32 (dt, J(H,H) = 1 and 7 Hz, 1H, 1CHar),
7.18 (d, J(H,H) = 7 Hz, 1H, 1CHar), 4.62 (dt, J(H,H) = 2 and 12 Hz, 1H, 1CH), 4.30 (t, J(H,H)
= 12 Hz, 1H, 1CH), 3.95 (dt, J(H,H) = 1 and 11 Hz, 1H, 1CH), 3.90-3.80 (m, 3H, 1CH2 and
1CH), 3.60-3.51 (m, 1H, 1CH), 3.26 (bd s, 1H, OH), 2.39 (hept, J(H,H) = 3 Hz, 1H, 1CH),
1.39 (s, 9H, 3CH3), 1.07 (d, J(H,H) = 7 Hz, 1H, 1CH3), 1.01 (d, J(H,H) = 7 Hz, 1H, 1CH3).
13C
NMR (100 MHz, CDCl3): = 159.2, 147.4, 134.1, 130.7, 129.5, 128.8, 128.1, 119.1 (q,
J(C,F) = 321.2 Hz), 65.0, 57.3, 54.8, 47.7, 35.6, 31.7 (3C), 26.7, 17.7, 14.4.
19F
NMR (376.5 MHz, CDCl3): = -79.9.
HRMS (FAB), calcd for C+: C18H29N2O: 289.2280, found: 289.2280.
3-(2-tert-Butyl-phenyl)-1-(3-hydroxy-propyl)-5-isopropyl-4,5-dihydro-3H-imidazol-1ium hexafluoro phosphate (4d):
Imidazole 3 (1.2 g, 5 mmol) was dissolved in acetone (5 mL) and 3-iodo-1-propanol (960 L,
10 mmol, 2 equiv.) was added and the reaction mixture was stirred at reflux for 12h. After
being cooled to room temperature, KPF6 (1.1 g, 6 mmol, 1.2 equiv.) was added at room
temperature. After 1h stirring, the solvent was evaporated under reduced pressure; the residue
was dissolved in dichloromethane and washed with brine. The organic layer was dried over
MgSO4 and concentrated in vacuo. Purification by flash chromatography (CH2Cl2/acetone
3/1) afforded the imidazolium salt 4d as a white solid (1.34 g, 60%, two steps).
Mp = 88-90°C (AcOEt).
[]D20 = +14.3 (c = 1 in chloroform).
1H
NMR (400 MHz, CD2Cl2): = 7.95 (s, 1H, 1CH), 7.58 (dd, J(H,H) = 2 and 7 Hz, 1H,
1CHar), 7.45 (dt, J(H,H) = 1 and 7 Hz, 1H, 1CHar), 7.34 (dt, J(H,H) = 1 and 7 Hz, 1H, 1CHar),
7.16 (dd, J(H,H) = 1 and 8 Hz, 1H, 1CHar), 4.60 (dt, J(H,H) = 3 and 11 Hz, 1H, 1CH), 4.28 (t,
J(H,H) = 12 Hz, 1H, 1CH), 3.93 (t, J(H,H) = 11 Hz, 1H, 1CH), 3.90 (m, 1H, 1CH), 3.77 (m,
2H, 1CH2), 3.59 (m, 1H, 1CH), 2.39 (hept, J(H,H) = 4 Hz, 1H, 1CH), 1.99-1.91 (m, 2H,
1CH2), 1.39 (s, 9H, 3CH3), 1.04 (d, J(H,H) = 8 Hz, 1H, 1CH3), 1.00 (d, J(H,H) = 8 Hz, 1H,
1CH3).
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Supplementary Material (ESI) for Chemical Communications
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13C
NMR (100 MHz, CD2Cl2): = 158.9, 147.8, 134.5, 131.0, 130.1, 129.3, 128.4, 65.2,
60.0, 55.3, 44.4, 35.9, 31.9, 28.9, 26.9, 18.0, 14.5.
19F
NMR (376.5 MHz, CD2Cl2): = -73.0 (d, J(F,P) = 711.1 Hz).
31P
NMR (162 MHz, CD2Cl2): = -143.3 (sept, J(P,F) = 711.1 Hz).
3-(2-tert-Butyl-phenyl)-1-(8-hydroxy-octyl)-5-isopropyl-4,5-dihydro-3H-imidazol-1-ium
hexafluoro phosphate (4e):
Imidazole 3 (1.2 g, 5 mmol) was dissolved in acetone (5 mL) and 8-bromo-1-octanol (1.71
mL, 10 mmol, 2 equiv.) was added and the reaction mixture was stirred at reflux for 72h.
After being cooled to room temperature, KPF6 (1.1 g, 6 mmol, 1.2 equiv.) was added at room
temperature. After 2h stirring, the solvent was evaporated under reduced pressure; the residue
was dissolved in dichloromethane and washed with brine. The organic layer was dried over
MgSO4 and concentrated in vacuo. Purification by flash chromatography (CH2Cl2/acetone
3/1) afforded the imidazolium salt 4e as a white solid (1.26 g, 50%, two steps).
[]D20 = +1.7 (c = 1.05 in chloroform).
1H
NMR (400 MHz, CD2Cl2): = 7.93 (s, 1H, 1CH), 7.59 (dd, J(H,H) = 1 and 8 Hz, 1H,
1CHar), 7.46 (dt, J(H,H) = 1 and 8 Hz, 1H, 1CHar), 7.35 (dt, J(H,H) = 1 and 8 Hz, 1H, 1CHar),
7.17 (d, J(H,H) = 8 Hz, 1H, 1CHar), 4.49 (dt, J(H,H) = 3 and 11 Hz, 1H, 1CH), 4.29 (t, J(H,H)
= 12 Hz, 1H, 1CH), 3.95 (t, J(H,H) = 12 Hz, 1H, 1CH), 3.70 (m, 1H, 1CH), 3.56 (m, 2H,
1CH2), 3.48 (m, 1H, 1CH), 2.37 (hept, J(H,H) = 4 Hz, 1H, 1CH), 1.78-1.63 (m, 2H, 1CH2),
1.55-1.47 (m, 2H, 1CH2) 1.39 (s, 9H, 3CH3), 1.39-1.30 (m, 8H, 4CH2), 1.05 (d, J(H,H) = 7
Hz, 1H, 1CH3), 0.99 (d, J(H,H) = 7 Hz, 1H, 1CH3).
13C
NMR (100 MHz, CD2Cl2): = 158.2, 147.6, 134.3, 131.1, 130.0, 129.3, 128.4, 65.1,
62.8, 55.0, 36.0, 32.8, 32.0, 29.3, 29.0, 27.3, 27.0, 26.4, 25.7, 17.9, 14.4.
19F
NMR (376.5 MHz, CD2Cl2): = -72.9 (d, J(F,P) = 712.8 Hz).
31P
NMR (162 MHz, CD2Cl2): = -143.2 (sept, J(P,F) = 712.8 Hz).
Representative procedure for NMR Experiment.
Without 18C6: 12.5 mg of (Rac)-potassium-2-methoxy-2-(trifluoromethyl)phenylacetate 5
and imidazolium salt 4 (3.3 equiv.) were dissolved in 0.4 mL of acetone d6 and the spectrum
was recorded. Recovery of imidazolium salt can be realised after dilution in dichloromethane
7
Supplementary Material (ESI) for Chemical Communications
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following by repeating washing with water. The organic layer was then dried over MgSO4 and
concentrated in vacuo to afford the pure imidazolium salt without any trace of Mosher salt.
With 18C6: the Mosher salt 5 was previously dissolved in 0.4 mL of CD2Cl2 in presence of
12.1 mg (1 equiv.) of crown ether 18C6, then imidazolium salt 4 (3.3 equiv.) was introduced
and the spectrum was recorded.
8
13
C NMR CDCl3
150
200
5
150
9
(ppm)
4
100
34.4318
30.5925
29.9379
28.2777
19.5613
6
O
NHBoc
40
20
3
50
2.4771
2.4619
4.1569
4.1436
4.1366
4.1220
5.0213
7.9806
7.6666
7.6494
7.4035
7.3838
7.2433
7.2249
7.2058
7.1715
7.1524
7.1340
1.0750
1.0579
0.9994
0.9829
60
3.0518
3.1605
H NMR CDCl3
1.4710
1.4100
80
9.1345
9.6049
1.0007
1.0843
1.0504
1.0602
1.0189
1.0439
NH
60.8523
7
80.3604
134.8857
126.7600
126.5205
125.9857
8
155.9263
9
1.0048
0.9036
1
169.9827
0
Integral
Supplementary Material (ESI) for Chemical Communications
100This journal is © The Royal Society of Chemistry 2004
2
1
(ppm)
100
50
0
0
150
1
H NMR CDCl200
3
150
10(ppm)
4
100
3
50
19.4017
18.0128
5
34.2004
32.9392
29.7783
6
2
1.9030
5.9192
9.0894
0.9903
2.0314
NH
1.0060
0.9461
2.0129
1.0784
0.9981
3.3307
3.3053
2.9220
2.8985
2.8712
2.8661
2.8591
2.8521
2.8426
2.8286
1.7697
1.7526
1.7386
1.7360
1.7221
1.7189
1.7049
1.6884
1.4793
1.1856
1.0318
1.0204
1.0147
1.0032
4.7341
7.2935
7.2897
7.2738
7.2700
7.1817
7.1772
7.1632
7.1613
7.1594
7.1429
7.1391
6.7368
6.7336
6.7177
6.7145
6.7050
6.7024
6.6993
6.6961
6.6853
This journal is © The Royal Society of Chemistry 2004
48.2248
7
56.3186
8
116.5909
111.5303
9
133.4250
127.0393
126.1054
146.8507
0
Integral
Supplementary Material (ESI) for Chemical Communications
100
80
60
NH2
40
2
20
1
(ppm)
100
50
0
0
13
150
C NMR CDCl3
200
150
11
(ppm)
4
100
3
50
19.4735
18.7871
5
35.4136
33.1308
31.3188
6
2
2.9333
3.0907
9.2610
1.0063
1.0228
N
1.0093
0.9779
0.9651
0.9933
1.9109
1.8944
1.8773
1.8601
1.8436
1.8264
1.4076
1.1038
1.0866
0.9747
0.9576
3.9753
3.9619
3.9550
3.9505
3.9372
3.9321
3.9251
3.9117
3.9073
3.7064
3.6823
3.6588
3.2113
3.1872
3.1624
7.4582
7.4513
7.4468
7.4405
7.4341
7.2574
7.2536
7.2460
7.2396
7.2345
7.0407
7.0286
7.0178
6.8106
6.8061
Supplementary Material (ESI) for Chemical Communications
58.2023
7
73.2165
8
141.8700
129.5856
127.7897
127.4544
127.3267
9
149.1176
-20
1.0000
2.2399
1
156.8283
0
Integral
100This journal is © The Royal Society of Chemistry 2004
80
H NMR CDCl3
60
40
N
3
20
1
(ppm)
100
50
0
0
200
C NMR CDCl3
13
150
200
150
12(ppm)
4
100
3
50
17.7334
14.4049
5
35.5813
31.6940
26.7212
6
47.6740
7
57.3163
54.7541
8
2
3.0102
2.7672
9.7696
1.0193
1.3209
1.2729
2.8941
0.9966
0.9456
N
64.9711
9
147.3935
134.0715
130.6871
129.5138
128.8034
128.0770
124.3574
121.1646
117.9718
114.7790
1
1.0000
1.0304
1.0139
1.0503
0.8866
60
159.2309
0
Integral
3.9720
3.9459
3.9173
3.9135
3.9002
3.8430
3.8366
3.5900
3.5805
3.5767
3.5563
3.5462
3.5360
3.5220
2.4053
2.3958
2.3881
2.3786
2.3716
1.3935
1.0725
1.0553
1.0153
0.9981
4.6552
4.6457
4.6260
4.6209
4.6006
4.5910
4.3286
4.2987
4.2694
8.0829
7.5655
7.5624
7.5452
7.5420
7.4480
7.4448
7.4295
7.4264
7.4098
7.4060
7.3431
7.3393
7.3240
7.3202
7.3056
7.3018
7.1893
7.1709
100Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
80
H NMR CDCl3
NTf2
40
N
OH
4c
20
1
(ppm)
100
50
0
0
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
-79.9047
160
140
19
F NMR CDCl3
NTf2
120
N
N
100
OH
80
4c
60
40
20
0
-50
-100
-150
-200
(ppm)
13
-250
200
13
C NMR CD2Cl2
150
200
5
150
14
(ppm)
4
100
3
50
17.9565
14.4763
6
35.9160
31.9170
28.9078
26.9123
7
2
3.0491
3.0852
9.4594
2.2651
1.1041
4d
1.2473
0.8622
2.1507
1.2061
N
1.1129
1.0788
1.0608
1.0496
1.0731
1.0289
60
44.4169
8
65.2021
59.9739
55.2565
9
147.7603
134.5261
131.0459
130.0641
129.2978
128.4278
-20
1.0000
1
158.8633
0
Integral
4.6363
4.6274
4.6058
4.5982
4.5816
4.5727
4.3115
4.2816
4.2518
3.9486
3.9194
3.9130
3.8971
3.8825
3.8761
3.7802
3.7770
3.7643
3.7522
3.7490
3.6276
3.6136
3.5997
3.5920
3.5774
3.5634
2.4143
2.4041
2.3965
2.3870
2.3794
2.3698
1.9948
1.9815
1.9376
1.9243
1.9097
1.3910
1.0580
1.0415
1.0091
0.9913
7.5974
7.5936
7.5771
7.5733
7.4748
7.4716
7.4563
7.4532
7.4366
7.4328
7.3661
7.3623
7.3470
7.3432
7.3280
7.3248
7.1780
7.1761
7.1589
7.1563
Supplementary Material (ESI) for Chemical Communications
100This journal is © The Royal Society of Chemistry 2004
80
H NMR CD2Cl2
PF6
N
40
OH
20
1
(ppm)
100
50
0
0
-72.0584
-73.9471
160Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry192004
F NMR
140
CD2Cl2
120
PF6
N
100
N
4d
80
OH
60
40
20
0
-50
-100
-150
-200
-250
-130.0744
-134.4616
-138.8623
-143.2495
-147.6367
-152.0374
-156.4247
(ppm)
160
31
P NMR CD2Cl2
140
120
100
80
60
40
20
0
150
100
50
0
-50
15
(ppm)
-100
-150
-200
-250
13
C NMR CD2Cl2
150
200
6
5
150
16
(ppm)
4
100
35.9559
32.8270
32.0288
29.2750
28.9876
27.2635
27.0081
26.4094
25.6831
17.8846
14.3566
7
3
50
2
2.8585
2.9149
1.9243
2.1197
9.2327
7.9651
1.1410
0.9584
1.9177
1.0621
20
0.9724
N
1.0360
0.9332
1.0193
1.0404
1.0554
1.0116
60
55.0170
8
65.0983
62.8314
9
147.5926
134.2626
131.0698
129.9763
129.3457
128.4038
-20
1.0000
1
158.2008
0
Integral
4.5340
4.5092
4.4882
4.4793
4.3185
4.2886
4.2588
3.9778
3.9492
3.9238
3.7287
3.7090
3.6931
3.6728
3.5673
3.5507
3.5342
3.4897
3.4821
3.4687
3.4541
3.4471
2.3959
2.3863
2.3787
2.3698
2.3622
2.3527
2.3355
1.7203
1.7006
1.5080
1.4915
1.3949
1.3453
1.3256
1.0593
1.0421
1.0059
0.9887
7.9254
7.6038
7.6006
7.5835
7.5803
7.4811
7.4773
7.4627
7.4595
7.4424
7.4392
7.3680
7.3648
7.3489
7.3458
7.3305
7.3267
7.1843
7.1652
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
100
80
H NMR CD2Cl2
PF6
N
40
4e
HO
1
(ppm)
200
100
50
0
0
-71.9612
-73.8579
180
Supplementary Material (ESI) for Chemical Communications
19
160
This journal is © The Royal Society of Chemistry
2004CD2Cl2
F NMR
140
120
PF6
100
N
N
80
4e
60
40
HO
20
0
-50
-100
-150
-200
-250
160
-130.0609
-134.4616
-138.8488
-143.2361
-147.6367
-152.0240
-156.4247
(ppm)
31
P NMR CD2Cl2
140
120
100
80
60
40
20
0
150
100
50
0
-50
17
(ppm)
-100
-150
-200
-250
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4a
18
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4a
19
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4b4b
20
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4b
21
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4c
22
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4c
23
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4d
24
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4d
25
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4e
26
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4c
27
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4c
28
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
29
Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2004
4a
30