10.1002/adsc.201801545
Advanced Synthesis & Catalysis
3H), 7.21 – 7.11 (m, 4H), 7.01 (d, J = 7.8 Hz, 1H), 6.77 (td, 65.1, 39.3, 38.9. IR (KBr) v 3060, 3029, 2956, 2924, 2853,
J = 7.9, 4.5 Hz, 1H), 4.15 – 3.88 (m, 2H), 3.14 – 2.98 (m, 1631, 1438, 1275, 1157, 1026, 867, 749, 699 cm-1. HRMS-
1H), 2.43 (dd, J = 6.5, 3.5 Hz, 1H), 2.12 (d, J = 3.5 Hz, 1H), ESI (m/z): calcd for C23H21I2N2O+ [M+H]+: 594.9738,
2.01 (d, J = 6.6 Hz, 1H).13C NMR (101 MHz, CDCl3) δ found 594.9742.
165.90 (d, JC-F = 2.2 Hz), 152.8, 150.8 (d, JC-F = 13.1 Hz),
150.3, 140.8, 139.7, 128.5, 128.2, 127.7, 127.5, 126.8,
2,4-Dibromo-6-((E)-(((R)-2-phenyl-2-((S)-2-
126.4, 120.3 (d, JC-F = 4.1 Hz), 118.6 (d, JC-F = 17.8 Hz),
phenylaziridin-1-yl)ethyl)imino)methyl)phenol
(3na)
117.6 (d, JC-F = 6.6 Hz), 74.8, 66.3, 39.3, 39.0. 19F NMR
(376 MHz, CDCl3) δ -137.9. IR (KBr) v 3062, 3030, 2956,
2925, 2853, 1637, 1467, 1378, 1276, 1250, 1089, 1027,
847, 749, 699 cm-1. HRMS-ESI (m/z): calcd for
C23H22FN2O+ [M+H]+: 361.1711, found 361.1713.
Yellow oil, 116 mg, yield 78%, Rf = 0.3 (PE/EA = 5:1, v/v),
25
1
[α] , = +14.4 (c 0.39, dichloromethane). H NMR (400
MHzD, CDCl3) δ 14.61 (s, 1H), 8.13 (s, 1H), 7.70 (d, J = 2.3
Hz, 1H), 7.36 (dd, J = 7.9, 1.3 Hz, 2H), 7.31 – 7.26 (m, 3H),
7.25 – 7.18 (m, 4H), 7.17 – 7.12 (m, 2H), 4.05 (dd, J = 12.2,
7.1 Hz, 1H), 3.98 (dd, J = 12.2, 4.6 Hz, 1H), 3.05 (dd, J =
6.8, 5.6 Hz, 1H), 2.42 (dd, J = 6.5, 3.5 Hz, 1H), 2.09 (d, J =
3.5 Hz, 1H), 1.97 (d, J = 6.6 Hz, 1H). 13C NMR (101 MHz,
4-Chloro-2-((E)-(((R)-2-phenyl-2-((S)-2-phenylaziridin-
1-yl)ethyl)imino)methyl)phenol (3ja)
Yellow solid, 79 mg, yield 70%, m.p. 125–127 oC, Rf = 0.5 CDCl3) δ 164.6, 159.1, 140.3, 139.6, 137.9, 132.8, 128.6,
25
,
(PE/EA
=
5:1, v/v), [α]
=
+36.8 (c 0.94, 128.2, 127.8, 127.5, 126.9, 126.3, 119.6, 112.8, 109.1, 74.5,
D
dichloromethane). 1H NMR (400 MHz, CDCl3) δ 13.42 (s, 65.5, 39.3, 39.0. IR (KBr) v 3062, 3030, 2961, 2925, 2853,
1H), 8.25 (s, 1H), 7.42 – 7.36 (m, 2H), 7.32 – 7.28 (m, 2H), 1634, 1495, 1447, 1377, 1261, 1207, 1024, 866, 800, 741,
7.28 – 7.22 (m, 4H), 7.20 (dd, J = 4.7, 2.1 Hz, 2H), 7.17 – 699 cm-1. HRMS-ESI (m/z): calcd for C23H21Br2N2O+
7.14 (m, 2H), 6.92 (d, J = 8.8 Hz, 1H), 4.08 – 3.95 (m, 2H), [M+H]+: 500.9995, found 500.9998.
3.04 (dd, J = 6.7, 5.9 Hz, 1H), 2.42 (dd, J = 6.5, 3.5 Hz,
1H), 2.10 (d, J = 3.5 Hz, 1H), 1.99 (d, J = 6.6 Hz, 1H). 13C
2-Bromo-4-nitro-6-((E)-(((R)-2-phenyl-2-((S)-2-
NMR (101 MHz, CDCl3) δ 165.1, 159.9, 140.9, 139.8,
phenylaziridin-1-yl)ethyl)imino)methyl)phenol
(3oa)
Yellow crystals, 105 mg, yield 75%, m.p. 193–196 oC, Rf =
132.2, 130.5, 128.4, 128.2, 127.6, 127.5, 126.8, 126.4,
123.2, 119.5, 118.7, 74.9, 66.8, 39.3, 39.0. IR (KBr) v 3061,
3030, 2957, 2924, 2853, 1634, 1576, 1479, 1378, 1278,
1202, 1090, 1026, 820, 745, 699 cm-1. HRMS-ESI (m/z):
calcd for C23H22ClN2O+ [M+H]+: 377.1415, found
377.1416.
25
0.5 (PE/EA = 1:1, v/v), [α]
,
= -95.0 (c 0.98,
D
dichloromethane). 1H NMR (400 MHz, CDCl3) δ 15.01 (s,
1H), 8.54 (d, J = 2.8 Hz, 1H), 8.09 (d, J = 2.8 Hz, 1H), 7.95
(s, 1H), 7.33 – 7.29 (m, 3H), 7.29 – 7.27 (m, 2H), 7.25 –
7.21 (m, 1H), 7.18 (d, J = 1.6 Hz, 1H), 7.16 (s, 1H), 4.06
(dd, J = 12.8, 4.8 Hz, 1H), 3.99 (dd, J = 12.8, 6.1 Hz, 1H),
2.49 (dd, J = 6.6, 3.5 Hz, 1H), 2.15 (d, J = 3.5 Hz, 1H),
1.97 (d, J = 6.7 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ
4-Bromo-2-((E)-(((R)-2-phenyl-2-((S)-2-phenylaziridin-
1-yl)ethyl)imino)methyl)phenol (3ka)
o
Yellow crystals, 99 mg, yield 71%, m.p. 118–120 C, Rf = 172.7, 166.3, 138.9, 138.4, 135.7, 132.2, 130.0, 128.9,
25
,
0.5 (PE/EA = 5:1, v/v), [α]
= +22.7 (c 1.13, 128.4, 127.4, 127.2, 126.2, 122.8, 117.7, 112.6, 73.3, 59.8,
D
dichloromethane). 1H NMR (400 MHz, CDCl3) δ 13.44 (s, 39.4, 39.3. IR (KBr) v 3061, 3031, 2956, 2924, 2853, 1649,
1H), 8.21 (s, 1H), 7.39 – 7.34 (m, 3H), 7.32 – 7.25 (m, 3H), 1599, 1543, 1494, 1452, 1317, 1218, 1093, 1028, 903, 746,
7.24 – 7.20 (m, 3H), 7.19 – 7.12 (m, 3H), 6.86 (d, J = 8.8 699 cm-1. HRMS-ESI (m/z): calcd for C23H21BrN3O3
+
Hz, 1H), 4.10 – 3.87 (m, 2H), 3.12 – 2.94 (m, 1H), 2.40 (dd, [M+H]+: 466.0761, found 466.0760.
J = 6.5, 3.5 Hz, 1H), 2.08 (d, J = 3.5 Hz, 1H), 1.96 (d, J =
6.6 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 165.0, 160.4,
2-((E)-(((R)-2-((S)-2-Benzylaziridin-1-yl)-3-
140.9, 139.8, 135.0, 133.5, 128.5, 128.2, 127.7, 127.5,
phenylpropyl)imino)methyl)phenol (3ab)
126.8, 126.4, 120.2, 119.1, 110.0, 74.9, 66.8, 39.3, 39.00.
Yellow oil, 77 mg, yield 67%, Rf = 0.3 (PE/EA = 1:1, v/v),
25
1
IR (KBr) v 3061, 3029, 2957, 2925, 2853, 1634, 1476,
[α] , = -115.6 (c 1.35, dichloromethane). H NMR (400
MHzD, CDCl3) δ 13.50 (s, 1H), 8.10 (s, 1H), 7.39 – 7.31 (m,
1H), 7.30 – 7.23 (m, 3H), 7.23 – 7.15 (m, 4H), 7.15 – 7.11
(m, 2H), 7.03 (d, J = 6.3 Hz, 3H), 6.87 (td, J = 7.5, 0.9 Hz,
1H), 3.80 – 3.59 (m, 1H), 3.17 – 3.01 (m, 2H), 2.88 (dd, J
= 13.5, 8.6 Hz, 1H), 2.72 (dd, J = 13.9, 4.7 Hz, 1H), 2.31
1366, 1277, 1202, 1088, 1027, 820, 750, 699 cm-1. HRMS-
ESI (m/z): calcd for C23H22BrN2O+ [M+H]+: 421.0910,
found 421.0912.
2,4-Di-tert-butyl-6-((E)-(((R)-2-phenyl-2-((S)-2-
phenylaziridin-1-yl)ethyl)imino)methyl)phenol
(3la) (dd, J = 14.0, 7.5 Hz, 1H), 2.15 (dd, J = 12.1, 8.3 Hz, 1H),
Yellow oil, 50 mg, yield 37%, Rf = 0.7 (PE/EA = 5:1, v/v), 1.69 (d, J = 3.5 Hz, 1H), 1.64 (dt, J = 8.1, 5.7 Hz, 1H), 1.37
25
1
[α] , = +37.5 (c 0.48, dichloromethane). H NMR (400 (d, J = 6.2 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 164.8,
MHzD, DMSO-d6) δ 14.03 (s, 1H), 8.48 (s, 1H), 7.37 (d, J = 161.2, 139.0, 138.1, 132.3, 131.4, 129.5, 128.7, 128.4,
7.1 Hz, 2H), 7.28 (d, J = 2.3 Hz, 1H), 7.24 – 7.19 (m, 4H), 128.3, 126.4, 126.2, 118.7, 118.7, 117.0, 72.5, 65.8, 42.1,
7.18 – 7.13 (m, 3H), 7.13 – 7.09 (m, 3H), 3.96 (dd, J = 12.5, 41.0, 39.5, 33.3. IR (KBr) v 3061, 3027, 2924, 2854, 1727,
6.8 Hz, 1H), 3.88 (dd, J = 12.4, 5.5 Hz, 1H), 3.07 (t, J = 6.1 1631, 1581, 1496, 1455, 1279, 1208, 1151, 1080, 804, 754,
Hz, 1H), 2.43 (dd, J = 6.3, 3.2 Hz, 1H), 2.03 (d, J = 6.6 Hz, 700 cm-1. HRMS-ESI (m/z): calcd for C25H27N2O+ [M+H]+:
1H), 1.91 (d, J = 3.2 Hz, 1H), 1.35 (s, 9H), 1.23 (s, 9H). 13C 371.2118, found 371.2125. HPLC analysis: Lux 5
NMR (101 MHz, DMSO-d6) δ 168.3, 158.4, 142.0, 140.8, cellulose-1 (i-PrOH/hexane = 10:90, v/v, 1.0 mL/min, 260
139.8, 136.1, 128.5, 127.9, 127.6, 127.0, 126.7, 126.6, nm), tR = 7.36 min, ee > 99%.
126.4, 118.2, 74.1, 65.6, 39.4, 38.9, 35.0, 34.3, 31.8, 29.7.
IR (KBr) v 3063, 3030, 2956, 2869, 1632, 1604, 1464,
2-((E)-(((R)-2-((S)-2-Benzylaziridin-1-yl)-3-
1361, 1275, 1204, 1026, 750, 699 cm-1. HRMS-ESI (m/z):
phenylpropyl)imino)methyl)-4-methoxyphenol (3cb)
calcd for C31H39N2O+ [M+H]+: 455.3057, found 455.3062.
Yellow oil, 86 mg, yield 72%, Rf = 0.5 (PE/EA = 1:1, v/v),
25
1
[α] , = -117.1 (c 0.68, dichloromethane). H NMR (400
MHzD, CDCl3) δ 12.99 (s, 1H), 8.06 (s, 1H), 7.30 – 7.18 (m,
2,4-Diiodo-6-((E)-(((R)-2-phenyl-2-((S)-2-
6H), 7.13 (d, J = 7.2 Hz, 2H), 7.04 (d, J = 6.9 Hz, 2H), 7.00
phenylaziridin-1-yl)ethyl)imino)methyl)phenol (3ma)
– 6.93 (m, 2H), 6.68 (d, J = 1.8 Hz, 1H), 3.77 (s, 3H), 3.72
o
Yellow crystals, 133 mg, yield 75%, m.p. 64–66 C, Rf =
25
,
– 3.63 (m, 1H), 3.08 (d, J = 4.2 Hz, 1H), 3.05 (d, J = 4.5
Hz, 1H), 2.87 (dd, J = 13.5, 8.6 Hz, 1H), 2.72 (dd, J = 13.9,
4.6 Hz, 1H), 2.30 (dd, J = 13.9, 7.5 Hz, 1H), 2.14 (dd, J =
12.1, 8.4 Hz, 1H), 1.69 (d, J = 3.5 Hz, 1H), 1.68 – 1.62 (m,
1H), 1.37 (d, J = 6.1 Hz, 1H). 13C NMR (101 MHz, CDCl3)
δ 164.6, 155.3, 152.0, 139.0, 138.1, 129.6, 128.8, 128.4,
128.4, 126.4, 126.2, 119.3, 118.4, 117.7, 115.0, 72.6, 65.82,
55.9, 42.2, 41.0, 39.5, 33.3. IR (KBr) v 3028, 2987, 2969,
2921, 2856, 1664, 1633, 1590, 1494, 1450, 1386, 1272,
1074, 1037, 759, 746, 700 cm-1. HRMS-ESI (m/z): calcd
0.4 (PE/EA = 5:1, v/v), [α]
= +41.5 (c 1.06,
D
dichloromethane). 1H NMR (400 MHz, CDCl3) δ 14.84 (s,
1H), 8.05 (d, J = 2.1 Hz, 1H), 8.02 (s, 1H), 7.44 (d, J = 2.1
Hz, 1H), 7.35 (dd, J = 7.9, 1.4 Hz, 2H), 7.31 – 7.25 (m, 3H),
7.25 – 7.18 (m, 3H), 7.17 – 7.12 (m, 2H), 4.03 (dd, J = 12.2,
7.2 Hz, 1H), 3.97 (dd, J = 12.3, 5.0 Hz, 1H), 3.04 (dd, J =
6.9, 5.5 Hz, 1H), 2.42 (dd, J = 6.5, 3.5 Hz, 1H), 2.08 (d, J =
3.5 Hz, 1H), 1.96 (d, J = 6.6 Hz, 1H). 13C NMR (101 MHz,
CDCl3) δ 164.3, 162.4, 149.0, 140.3, 139.9, 139.56, 128.6,
128.2, 127.8, 127.4, 126.9, 126.3, 119.4, 89.0, 78.3, 74.5,
9
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