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E. Bellur, P. Langer / Tetrahedron 62 (2006) 5426–5434
isolated after chromatography (silica gel, n-hexane/
EtOAc¼100:1/1:1) as a yellow oil (0.081 g, 55%). H
79.2 (OCH), 113.5 (CH]C–N), 127.1 (2C), 128.0 (2C),
128.2 (2C), 128.27, 128.34, 128.7 (2C, CH of Ph), 137.1,
137.9 (C of Ph), 163.8 (C–Ph), 164.2 (N]C–N), 169.9
(N–C]CH). IR (neat, cmꢁ1): ~n¼3063 (w), 2944 (w),
1647 (s), 1572 (s), 1533 (s), 1495 (w), 1447 (m), 1424 (w),
1373 (s), 1327 (m), 1285 (w), 1258 (m), 1176 (w), 1082
(m), 1066 (m), 1027 (m), 991 (w), 920 (w), 909 (w), 868
(w), 779 (w), 748 (m), 694 (s). UV–vis (CH3CN, nm):
lmax (log 3)¼255 (4.54). MS (EI, 70 eV): m/z (%)¼302
([M–Br]+, 3), 300 (11), 285 (18), 284 (68), 283 (27), 271
(21), 259 (30), 246 (100), 234 (2), 232 (1), 142 (7), 128
(4), 117 (15), 104 (30), 77 (30).
1
NMR (CDCl3, 300 MHz): d¼1.25 (t, J¼7.2 Hz, 3H, CH3),
1.51–1.63 (m, 2H, CH2), 1.92–2.05 (m, 2H, CH2), 2.92 (t,
J¼7.8 Hz, 2H, CH2), 3.81–3.91 (m, 1H, OCH), 7.37–7.53
(m, 7H, CH]C, 6ꢂCH of Ph), 8.19–8.22 (m, 2H, 2ꢂCH
of Ph), 8.57–8.60 (m, 2H, 2ꢂCH of Ph). 13C NMR
(CDCl3, 75 MHz): dC¼23.5 (CH3), 24.8, 37.8, 38.6 (CH2),
67.7 (OCH), 113.4 (CH]C–N), 127.1 (2C), 128.3 (2C),
128.4 (2C), 128.8 (2C), 130.4, 130.6 (CH of Ph), 137.2,
138.1 (C of Ph), 163.7 (C–Ph), 164.2 (N]C–N), 171.1
(N–C]CH). IR (neat, cmꢁ1): ~n¼3382 (br), 3064 (w),
2974 (s), 2931 (m), 2865 (s), 2810 (w), 1721 (m), 1575
(s), 1532 (s), 1493 (m), 1451 (m), 1375 (s), 1314 (m),
1309 (m), 1278 (s), 1172 (m), 1118 (s), 1077 (m), 1029
(w), 921 (w), 841 (w), 746 (s), 697 (s), 637 (w). UV–vis
(CH3CN, nm): lmax (log 3)¼256 (4.41). MS (EI, 70 eV):
m/z (%)¼318 (M+, 1), 273 (16), 259 (14), 146 (100), 233
(2), 216 (31), 202 (5), 174 (28), 158 (5), 143 (6), 133 (16),
128 (5), 120 (17), 114 (9), 106 (14), 104 (83), 91 (6), 77
(41). Anal. Calcd for C21H22N2O (318.418): C 79.21, H
6.96, N 8.89. Found: C 78.99, H 7.01, N 8.64.
3.1.4.12.
3-(2,6-Diphenylpyrimidin-4-yl)-2-methyl-
propan-1-ol (11f). Starting with 9a (0.500 g, 2.5 mmol),
benzamidine hydrochloride monohydrate (3a) (4.370 g,
25 mmol) and NEt3 (3.4 mL, 25 mmol) in ethanol
(25 mL), 11f was isolated after chromatography (silica gel,
n-hexane/EtOAc¼100:1/1:1) as a yellow oil (0.381 g,
1
50%). H NMR (CDCl3, 300 MHz): d¼1.03 (d, J¼6.9 Hz,
3H, CH3), 2.28–2.37 (m, 1H, CH2), 2.82–2.89 (m, 1H,
CH2), 2.93–2.99 (m, 1H, CH2), 3.48 (dd, J¼11.1, 6.9 Hz,
1H, OCH2), 3.63 (dd, J¼11.1, 5.1 Hz, 1H, OCH2), 7.35–
7.53 (m, 7H, CH]C, 6ꢂCH of Ph), 8.15–8.22 (m, 2H,
2ꢂCH of Ph), 8.52–8.60 (m, 2H, 2ꢂCH of Ph). 13C NMR
(CDCl3, 75 MHz): dC¼17.9 (CH3), 35.4 (CH), 41.8 (CH2),
66.9 (OCH2), 114.4 (CH]C–N), 127.2 (2C), 128.2 (2C),
128.5 (2C), 128.8 (2C), 130.6, 130.8 (CH of Ph), 137.0,
137.7 (C of Ph), 163.7 (C–Ph), 164.0 (N]C–N), 169.6
(N–C]CH). IR (neat, cmꢁ1): ~n¼3338 (br), 3064 (w),
2966 (m), 2926 (m), 2872 (w), 1632 (w), 1574 (s), 1533
(s), 1498 (w), 1451 (m), 1374 (s), 1278 (w), 1176 (w),
1111 (m), 1075 (m), 1035 (m), 751 (m), 695 (s), 636 (w).
UV–vis (CH3CN, nm): lmax (log 3)¼256 (4.47). MS (EI,
70 eV): m/z (%)¼303 (M+, 1), 289 (1), 287 (4), 273 (3),
259 (12), 246 (100), 143 (7), 128 (4), 114 (5), 104 (23).
Anal. Calcd for C20H20N2O (304.391): C 78.92, H 6.62, N
9.20. Found: C 78.73, H 6.59, N 9.15.
3.1.4.10.
1-Chloro-4-(2,6-diphenylpyrimidin-4-yl)-
butan-2-ol (11d). Starting with 8c (0.100 g, 0.42 mmol),
benzamidine hydrochloride monohydrate (3a) (0.725 g,
4.2 mmol) and NEt3 (0.6 mL, 4.2 mmol) in ethanol
(5 mL), 11d was isolated after chromatography (silica gel,
n-hexane/EtOAc¼100:1/1:1) as a yellow solid (0.120 g,
85%), mp¼62.6 ꢀC. 1H NMR (CDCl3, 300 MHz):
d¼2.28–2.36 (m, 2H, CH2), 3.02–3.12 (m, 2H, CH2), 3.81
(dd, J¼14.7, 7.2 Hz, 1H, CH2–Cl), 4.22 (dd, J¼14.7,
9.6 Hz, 1H, CH2–Cl), 4.87–4.94 (m, 1H, OCH), 7.37–7.54
(m, 5H, 5ꢂCH), 7.93–7.96 (m, 2H, 2ꢂCH), 8.19–8.22 (m,
2H, 2ꢂCH), 8.58–8.62 (m, 2H, 2ꢂCH). 13C NMR
(CDCl3, 75 MHz): dC¼33.7, 34.0 (CH2), 60.0 (CH2–Cl),
79.2 (OCH2), 113.5 (CH]C–N), 127.1 (2C), 128.1, 128.2
(2C), 128.3, 128.4 (2C), 128.8 (2C, CH of Ph), 137.1,
138.0 (C of Ph), 163.9 (C–Ph), 164.2 (N]C–N), 169.9
(N–C]CH). IR (neat, cmꢁ1): ~n¼3064 (w), 2970 (w),
2931 (w), 2865 (w), 1648 (m), 1575 (s), 1534 (s), 1495
(w), 1448 (w), 1374 (s), 1260 (w), 1174 (w), 1116 (m),
1072 (m), 1028 (w), 778 (m), 750 (m), 695 (s). UV–vis
(CH3CN, nm): lmax (log 3)¼256 (4.44). MS (EI, 70 eV):
m/z (%)¼302 ([M–Cl]+, 15), 261 (30), 257 (14), 233 (4),
215 (100), 195 (5), 169 (3), 159 (24), 141 (4), 128 (13),
119 (3), 117 (21), 91 (22), 86 (20), 84 (37), 79 (4), 77
(16). Anal. Calcd for C20H19ClN2O (338.837): C 70.90, H
5.65, N 8.27. Found: C 71.17, H 6.11, N 8.25.
3.1.4.13. 2-Methyl-3-(2-methyl-6-phenylpyrimidin-4-
yl)propan-1-ol (11g). Starting with 9a (0.708 g,
3.5 mmol), acetamidine hydrochloride (3b) (3.483 g,
35 mmol) and NEt3 (4.9 mL, 35 mmol) in ethanol
(35 mL), 11g was isolated after chromatography (silica
gel, n-hexane/EtOAc¼100:1/EtOAc), as a pale yellow
1
oil (0.395 g, 47%). H NMR (CDCl3, 300 MHz): d¼1.01
(d, J¼6.6 Hz, 3H, CH3), 2.01–2.14 (m, 1H, CH), 2.46 (dd,
J¼12.9, 5.7 Hz, 1H, CH2), 2.76 (s, 3H, CH3), 2.85 (dd,
J¼18.3, 5.7 Hz, 1H, CH2), 3.48 (dd, J¼10.5, 6.6 Hz, 1H,
OCH2), 3.61 (dd, J¼10.8, 4.5 Hz, 1H, OCH2), 7.38–7.44
(m, 4H, CH]C, 3ꢂCH of Ph), 7.85–7.88 (m, 2H, 2ꢂCH
of Ph). 13C NMR (CDCl3, 75 MHz): dC¼16.4, 25.8 (CH3),
35.2 (CH), 40.3 (CH2), 66.2 (OCH2), 113.8 (CH]C–N),
126.8 (2C), 127.0, 128.0 (2C, CH of Ph), 136.6 (C of Ph),
164.1 (C–Ph), 167.3 (N]C–N), 169.3 (N–C]CH). IR
(neat, cmꢁ1): ~n¼3346 (br), 3065 (w), 2963 (m), 2927 (m),
2874 (w), 1604 (s), 1529 (s), 1450 (m), 1419 (m), 1375
(m), 1325 (s), 1286 (s), 1182 (w), 1123 (w), 1074 (m),
1040 (m), 743 (s), 696 (m), 648 (w). UV–vis (CH3CN,
nm): lmax (log 3)¼244 (3.99), 277 (3.89), 325 (4.03). MS
(EI, 70 eV): m/z (%)¼242 (M+, 100), 197 (5), 184 (93),
173 (20), 148 (5), 105 (14), 77 (19), 57 (22). HRMS (ESI):
calcd for C15H18N2O [M+]: 241.1335; found: 241.1332.
3.1.4.11.
1-Bromo-4-(2,6-diphenylpyrimidin-4-yl)-
butan-2-ol (11e). Starting with 8d (0.100 g, 0.36 mmol),
benzamidine hydrochloride monohydrate (3a) (0.629 g,
3.6 mmol) and NEt3 (0.49 mL, 3.6 mmol in ethanol
(5 mL), 11e was isolated after chromatography (silica gel,
n-hexane/EtOAc¼100:1/1:1) as a yellow solid (0.109 g,
79%), mp¼111.3 ꢀC. 1H NMR (CDCl3, 300 MHz):
d¼2.27–2.35 (m, 2H, CH2), 3.01–3.14 (m, 2H, CH2), 3.80
(dd, J¼14.7, 7.2 Hz, 1H, CH2–Br), 4.21 (dd, J¼14.7,
9.6 Hz, 1H, CH2–Br), 4.84–4.91 (m, 1H, OCH), 7.36–7.54
(m, 5H, 5ꢂCH), 7.92–7.95 (m, 2H, 2ꢂCH), 8.19–8.22 (m,
2H, 2ꢂCH), 8.58–8.62 (m, 2H, 2ꢂCH). 13C NMR
(CDCl3, 75 MHz): dC¼33.7, 33.9 (CH2), 60.0 (CH2–Br),