7
HRMS (ESI+): m/z calcd. for C41H43N4OS [M-Br]+: 639.3152,
found: 639.3154.
13C-NMR (75 MHz, CDCl3, 298 K): δ / ppm = 152.9, 147.6,
145.1, 141.0, 139.8, 137.6, 135.8, 135.5, 133.8, 132.0, 131.5,
130.8, 129.6, 129.5, 129.3, 129.1, 126.1, 125.3, 123.5, 121.6,
119.2, 118.4, 107.2, 72.9, 72.0, 66.5, 62.9, 60.1, 50.5, 37.5, 26.4,
25.0, 22.4; 19F-NMR (282 MHz, CDCl3, 298 K): δ / ppm = -62.8;
HRMS (ESI+): m/z calcd. for C42H39F6N4O2 [M-Br]+: 745.2972,
found: 745.2975.
Ammonium salt A3: Obtained in 59% yield (14.5 mg) starting
1
from 20 mg (0.035 mmol) of the corresponding amine 11c. H-
NMR (300 MHz, CDCl3, 298.0 K): δ / ppm = 11.84 (s, 1 H), 9.60
(s, 1 H), 9.02 (dd, J1 = 1.9 Hz, J2 = 9.2 Hz, 1 H), 8.91 (d, J =
4.4 Hz, 1 H), 8.16 (d, J = 9.2 Hz, 1 H), 8.09 (d, J = 1.8 Hz, 1 H),
7.70 (d, J = 7.5 Hz, 2 H), 7.58 (d, J = 4.5 Hz, 1 H), 7.53-7.39 (m,
11 H), 7.32 (t, J = 7.6 Hz, 2 H), 6.10 (s, 1 H), 5.70 (d, J =
11.6 Hz, 1 H), 5.63-5.52 (m, 1 H), 5.36 (d, J = 17.2 Hz, 1 H),
5.05 (dd, J1 = 1.2 Hz, J2 = 10.4 Hz, 1 H), 4.96 (d, J = 11.9 Hz, 1
H), 4.44-4.28 (m, 3 H), 4.14-4.08 (m, 1 H), 3.89 (d, J = 11.7 Hz,
1 H), 3.18-3.10 (m, 2 H), 2.54 (bs, 1 H), 2.16-2.07 (m, 4 H),
1.46-1.38 (m, 1 H); 13C-NMR (75 MHz, CDCl3, 298 K): δ / ppm
= 179.8, 148.2, 146.0, 140.4, 139.1, 137.9, 135.9, 135.5, 134.0,
130.8, 130.4, 129.8, 129.4, 129.3, 128.4, 127.4, 126.4, 125.3,
124.9, 119.0, 118.7, 112.1, 72.6, 71.7, 66.6, 62.6, 60.3, 50.6,
37.6, 26.6, 25.1, 22.5; HRMS (ESI+): m/z calcd. for C40H41N4OS
[M-Br]+: 625.2996, found: 625.2999.
Ammonium salt A7: Obtained in 85% yield (124 mg) starting
from 100 mg (0.16 mmol) of the corresponding amine 11n. H-
1
NMR (300 MHz, CDCl3, 298.0 K): δ / ppm = 11.66 (s, 1 H),
10.15 (s, 1 H), 8.93 (d, J = 4.5 Hz, 1 H), 8.70 (d, J = 9.0 Hz, 1
H), 8.30 (s, 1 H), 8.25 (s, 2 H), 8.07 (d, J = 9.4 Hz, 1 H), 7.70-
7.41 (m, 11 H), 6.22 (s, 1 H), 5.71 (d, J = 12.0 Hz, 1 H), 5.57
(ddd, J1 = 16.8 Hz, J2 = 10.3 Hz, J3 = 5.9 Hz, 1 H), 5.36-5.30 (m,
1 H), 5.06 (d, J = 10.3 Hz, 1 H), 5.00 (d, J = 12.0 Hz, 1 H), 4.46
(d, J = 11.8 Hz, 1 H), 4.32-4.16 (m, 3 H), 4.05 (d, J = 11.8 Hz, 1
H), 3.17-3.04 (m, 2 H), 2.58 (bs, 1 H), 2.25-2.05 (m, 2 H), 1.83-
1.70 (m, 2 H), 1.47-1.41 (m, 1 H); 13C-NMR (75 MHz, CDCl3,
298 K): δ / ppm = 179.2, 148.6, 146.0, 140.6, 139.3, 138.1,
135.5, 134.3, 131.5, 131.1, 130.6, 130.1, 129.7, 129.5, 126.7,
126.2, 124.9, 123.5, 121.6, 121.4, 119.3, 118.7, 117.8, 112.1,
72.3, 71.7, 67.2, 62.1, 60.5, 51.0, 37.5, 26.3, 24.9, 22.3; 19F-NMR
(282 MHz, CDCl3, 298 K): δ / ppm = -62.8, -63.2; HRMS
(ESI+): m/z calcd. for C43H38F9N4OS [M-Br]+: 829.2617, found:
829.2625.
Ammonium salt A4: Obtained in 47% yield (11.2 mg) starting
1
from 20 mg (0.035 mmol) of the corresponding amine 11c. H-
NMR (300 MHz, CDCl3, 298.0 K): δ / ppm = 10.65 (s, 1 H), 8.85
(d, J = 4.5 Hz, 1 H), 8.71 (dd, J1 = 1.8 Hz, J2 = 9.2 Hz, 1 H), 8.38
(s, 1 H), 8.12 (d, J = 9.3 Hz, 1 H), 7.91 (s, 1 H), 7.60-7.42 (m,
16 H), 6.08 (s, 1 H), 5.80 (d, J = 11.8 Hz, 1 H), 5.64-5.53 (m,
1 H), 5.42 (d, J = 17.5 Hz, 1 H), 5.07 (dd, J1 = 1.2 Hz, J2 =
10.3 Hz, 1 H), 4.95 (d, J = 11.7 Hz, 1 H), 4.43 (d, J = 11.8 Hz,
1 H), 4.37-4.31 (m, 1 H), 4.16-4.10 (m, 1 H), 4.03 (d, J =
11.7 Hz, 1 H), 3.21-3.13 (m, 2 H), 2.58 (bs, 1 H), 2.16-2.08 (m,
3 H), 1.77-1.71 (m, 1 H), 1.47-1.42 (m, 1 H); 13C-NMR (75
MHz, CDCl3, 298 K): δ / ppm = 153.6, 147.3, 141.1, 139.6,
137.4, 135.9, 135.8, 134.2, 131.5, 130.9, 129.8, 129.7, 129.4,
128.8, 126.6, 125.5, 124.1, 122.5, 119.4, 119.1, 118.7, 106.9,
73.2, 72.0, 66.6, 62.8, 60.1, 50.6, 37.7, 26.6, 25.3, 22.6; HRMS
(ESI+): m/z calcd. for C40H41N4O2 [M-Br]+: 609.3224, found:
609.3224.
Ammonium salt A8: Obtained in 61% yield (66 mg) starting
from 75 mg (0.12 mmol) of the corresponding amine 11q. H-
1
NMR (300 MHz, CDCl3, 298.0 K): δ / ppm = 11.95 (s, 1 H),
10.56 (s, 1 H), 8.92 (d, J = 4.5 Hz, 1 H), 8.63 (d, J = 9.2 Hz, 1
H), 8.40 (s, 1 H), 8.32 (s, 2 H), 8.11 (d, J = 9.2 Hz, 1 H), 7.66-
7.35 (m, 11 H), 6.15 (s, 1 H), 5.56-5.42 (m, 2 H), 5.30-5.25 (m, 1
H), 5.01 (d, J = 10.8 Hz, 1 H), 4.97 (d, J = 11.7 Hz, 1 H), 4.42 (d,
J = 11.6 Hz, 1 H), 4.24-4.18 (m, 1 H), 4.17-3.99 (m, 2 H), 3.91
(d, J = 11.9 Hz, 1 H), 3.23-3.15 (m, 2 H), 2.57 (bs, 1 H), 2.20-
2.06 (m, 3 H), 1.81-1.71 (m, 1 H), 1.46-1.38 (m, 1 H), 1.32 (s, 9
H); 13C-NMR (75 MHz, CDCl3, 298 K): δ / ppm = 179.1, 154.4,
148.6, 146.0, 140.8, 139.2, 138.3, 135.9, 135.3, 133.3, 131.5,
131.0, 130.7, 129.6, 129.4, 126.6, 126.4, 125.1, 124.8, 123.5,
122.8, 121.5, 119.2, 118.4, 112.1, 72.2, 71.6, 67.0, 63.0, 60.4,
50.5, 37.5, 34.9, 31.1, 26.4, 25.0, 22.2; 19F-NMR (282 MHz,
CDCl3, 298 K): δ / ppm = -62.7; HRMS (ESI+): m/z calcd. for
C46H47F6N4OS [M-Br]+: 817.3369, found: 817.3372.
Ammonium salt A5: Obtained in 64% yield (16.5 mg) starting
1
from 20 mg (0.035 mmol) of the corresponding amine 11c. H-
NMR (300 MHz, CDCl3, 298.0 K): δ / ppm = 10.59 (s, 1 H), 9.19
(s, 1 H), 8.83 (d, J = 4.4 Hz, 1 H), 8.49-8.47 (m, 1 H), 8.25 (d, J
= 9.1 Hz, 1 H), 8.08 (s, 1 H), 7.95 (d, J = 9.2 Hz, 1 H), 7.72 (dd,
J1 = 1.4 Hz, J2 = 8.1 Hz, 1 H), 7.60 (dd, J1 = 1.2 Hz, J2 = 8.1 Hz,
1 H), 7.55 (d, J = 5.0 Hz, 2 H), 7.50-7.48 (m, 5 H), 7.47-7.40 (m,
5 H), 6.31 (s, 1 H), 5.62-5.51 (m, 2 H), 5.35-5.28 (m, 1 H), 5.04
(dd, J1 = 1.3 Hz, J2 = 10.5 Hz, 1 H), 4.95 (d, J = 11.6 Hz, 1 H),
4.68 (d, J = 11.6 Hz, 1 H), 4.43 (d, J = 11.8 Hz, 1 H), 4.31 (t, J =
9.3 Hz, 1 H), 4.18-4.08 (m, 2 H), 3.29-3.14 (m, 2 H), 2.57 (bs,
1 H), 2.21-2.08 (m, 3 H), 1.50-1.42 (m, 1 H), 1.25-1.20 (m, 1 H);
13C-NMR (75 MHz, CDCl3, 298 K): δ / ppm = 153.3, 148.6,
147.6, 145.1, 141.0, 139.9, 137.9, 136.0, 135.9, 134.1, 131.4,
130.9, 129.7, 129.5, 129.3, 129.2, 126.5, 125.4, 124.7, 123.7,
119.1, 118.5, 116.7, 113.3, 107.3, 72.9, 71.8, 67.2, 63.7, 60.2,
50.5, 37.7, 26.6, 25.2, 22.2; HRMS (ESI+): m/z calcd. for
C40H40N5O4 [M-Br]+: 654.3075, found: 654.3076.
Ammonium salt A9: Obtained in 61% yield (58 mg) starting
from 77 mg (0.12 mmol) of the corresponding amine 11p. H-
1
NMR (300 MHz, CDCl3, 298.0 K): δ / ppm = 11.86 (s, 1 H),
10.28 (s, 1 H), 8.94 (d, J = 4.4 Hz, 1 H), 8.79 (d, J = 9.4 Hz, 1
H), 8.30 (s, 3 H), 8.12 (d, J = 9.2 Hz, 1 H), 7.72-7.39 (m, 16 H),
6.19 (s, 1 H), 5.66-5.51 (m, 2 H), 5.36-5.30 (m, 1 H), 5.06-4.97
(m, 2 H), 4.41 (d, J = 11.8 Hz, 1 H), 4.27-4.09 (m, 3 H), 4.03 (d,
J = 11.7 Hz, 1 H), 3.29-3.16 (m, 2 H), 2.58 (bs, 1 H), 2.20-2.16
(m, 2 H), 1.80-1.71 (m, 2 H), 1.48-1.39 (m, 1 H); 13C-NMR (75
MHz, CDCl3, 298 K): δ / ppm = 179.2, 148.6, 142.3, 140.7,
139.4, 138.2, 135.8, 135.4, 132.6, 132.2, 131.5, 131.1, 130.7,
129.9, 129.7, 129.5, 129.4, 129.1, 128.2, 127.2, 126.7, 126.6,
125.1, 124.9, 123.6, 121.5, 119.3, 118.5, 117.8, 112.0, 72.5, 71.8,
66.9, 63.0, 60.5, 50.7, 37.5, 26.4, 25.0, 22.4; 19F-NMR
(282 MHz, CDCl3, 298 K): δ / ppm = -62.7; HRMS (ESI+): m/z
calcd. for C48H43F6N4OS [M-Br]+: 837.3056, found: 837.3061.
Ammonium salt A6: Obtained in 46% yield (61 mg) starting
1
from 89 mg (0.16 mmol) of the corresponding amine 11c. H-
NMR (300 MHz, CDCl3, 298.0 K): δ / ppm = 10.63 (s, 1 H), 8.96
(s, 1 H), 8.85 (d, J = 4.5 Hz, 1 H), 8.54 (d, J = 9.5 Hz, 1 H), 8.08
(d, J = 9.3 Hz, 1 H), 8.04 (s, 2 H), 7.94 (d, J = 1.7 Hz, 1 H), 7.58
(d, J = 4.5 Hz, 1 H), 7.53-7.39 (m, 11 H), 6.15 (s, 1 H), 5.64-5.52
(m, 2 H), 5.42-5.36 (m, 1 H), 5.04 (dd, J1 = 10.3 Hz, J2 = 1.1 Hz,
1 H), 4.95 (d, J = 11.7 Hz, 1 H), 4.46 (d, J = 11.7 Hz, 1 H), 4.31-
4.26 (m, 2 H), 4.14-4.00 (m, 2 H), 3.25-3.13 (m, 2 H), 2.58 (bs, 1
H), 2.17-1.90 (m, 3 H), 1.78-1.67 (m, 1 H), 1.47-1.39 (m, 1 H);
Ammonium salt A10: Obtained in 37% yield (26 mg) starting
1
from 47 mg (0.08 mmol) of the corresponding amine 11o. H-
NMR (300 MHz, CDCl3, 298.0 K): δ / ppm = 12.03 (s, 1 H),
10.30 (s, 1 H), 8.96 (d, J = 4.5 Hz, 1 H), 8.90 (d, J = 9.2 Hz, 1
H), 8.32 (s, 2 H), 8.26 (s, 1 H), 8.18 (d, J = 9.5 Hz, 1 H), 7.94-
7.45 (m, 15 H), 6.20 (s, 1 H), 5.72 (d, J = 11.0 Hz, 1 H), 5.58