Stereoselective Synthesis of syn- and anti-N-tert-Alkylamines
cm-1. Anal. Calcd for C22H28N2O: C, 78.53; H, 8.39; N, 8.33.
Found: C, 78.60; H, 8.48; N, 8.27.
N′-[1-(4-Ch lor oph en yl)-1-eth yl-2-m eth ylbu t-3-en yl]ben -
zoh yd r a zid e (a n ti-3h ): Mp 94-95 °C. H NMR (300 MHz,
1
CDCl3) δ 0.82-0.88 (m, 6H), 1.89 (qd, J ) 1.4, 7.5 Hz, 2H),
2.54 (qd, J ) 7.5 Hz, 1H), 4.96-5.04 (m, 2H), 5.37 (br, 1H),
5.52 (ddd, J ) 8.4, 9.8, 18.5 Hz, 1H), 7.06 (br, 1H), 7.19-7.63
(m, 9H); 13C NMR (300 MHz, CDCl3) δ 7.8, 14.9, 26.2, 44.6,
68.8, 115.9, 126.7, 128.1, 128.6, 129.2, 131.6, 132.7, 132.8,
139.3, 140.0, 165.7. IR (KBr) 3295, 1832, 1638, 1550, 1492,
N′-(1-Bu tyl-2-m eth yl-1-p h en ylbu t-3-en yl)ben zoh yd r a -
zid e (syn -3d ): Mp 85 °C. H NMR (300 MHz, CDCl3) δ 0.80
1
(t, J ) 7.3 Hz, 3H), 0.81 (d, J ) 7.0 Hz, 3H), 1.19-1.25 (m,
2H), 1.28-1.33 (m, 2H), 1.75-1.85 (m, 1H), 1.92-2.00 (m, 1H),
2.54 (qd, J ) 7.0 Hz, 1H), 5.00 (apparent d, J ) 10.3 Hz, 1H),
5.07 (apparent d, J ) 17.1 Hz, 1H), 5.56 (br, 1H), 5.68-5.77
(m, 1H), 7.09 (br, 1H), 7.14-7.56 (m, 10H); 13C NMR (300 MHz,
CDCl3) δ 14.0, 15.7, 23.3, 25.3, 33.7, 45.2, 67.2, 115.0, 126.6,
126.7, 127.5, 128.0, 128.6, 131.4, 133.2, 140.8, 141.0, 165.5.
IR (KBr) 3303, 1577, 1308, 923 cm-1. Anal. Calcd for
1449, 1319, 1097, 1014, 911 cm-1. Anal. Calcd for C20H23
-
ClN2O: C, 70.06; H, 6.76; N, 8.17. Found: C, 69.87; H, 6.91;
N, 8.16.
N′-[1-(4-Ch lor oph en yl)-1-eth yl-2-m eth ylbu t-3-en yl]ben -
zoh yd r a zid e (syn -3h ): Mp 149 °C.1H NMR (300 MHz, CDCl3)
δ 0.79 (d, J ) 7.0 Hz, 3H), 0.88 (t, J ) 7.3 Hz, 3H), 1.78-2.03
(m, 2H), 2.52 (qd, J ) 7.7 Hz, 1H), 5.00-5.10 (m, 2H), 5.58
(br, 1H), 5.71 (ddd, J ) 8.6, 10.1, 17.2 Hz, 1H), 7.13 (br, 1H),
7.25-7.56 (m, 9H); 13C NMR (400 MHz, CDCl3) δ 7.8, 15.7,
26.0, 44.8, 67.3, 115.2, 126.6, 128.1, 128.7, 129.2, 131.6, 132.7,
132.8, 139.0, 140.7, 165.8. IR (KBr) 3296, 1830, 1638, 1550,
1097, 1014, 911 cm-1. Anal. Calcd for C20H23ClN2O: C, 70.06;
H, 6.76; N, 8.17. Found: C, 70.52; H, 7.10; N, 7.84.
C
22H28N2O: C, 78.53; H, 8.39; N, 8.33. Found: C, 78.51; H,
8.35; N, 8.29.
N′-(1,2-Dim et h yl-1-n a p h t h a len -2-ylb u t -3-en yl)b en zo-
h yd r a zid e (a n ti-3e): Mp 149-150 °C. 1H NMR (400 MHz,
CDCl3) δ 0.70 (d, J ) 7.1 Hz, 3H), 1.53 (s, 3H), 2.64 (qd, J )
7.1 Hz, 1H), 5.19-5.28 (m, 2H), 5.70 (brd, J ) 8.5 Hz, 1H),
5.79-5.88 (m, 1H), 6.89 (brd, J ) 8.1 Hz, 1H), 7.03-7.84 (m,
12H); 13C NMR (400 MHz, CDCl3) δ 15.9, 16.7, 48.2, 64.9,
117.9, 125.1, 126.0, 126.1, 126.4, 126.6, 127.4, 128.16, 128.18,
128.5, 131.5, 132.4, 132.7, 133.2, 139.5, 141.6, 166.3. IR (KBr)
3266, 1625, 1546, 1508, 1449, 1227, 1201, 1135, 1119, 1019,
923 cm-1. Anal. Calcd for C23H24N2O: C, 80.20; H, 7.01; N,
8.13. Found: C, 80.16; H, 7.17; N, 8.11.
N′-[1-(4-Ch lor op h en yl)-2-m et h yl-1-p r op ylbu t -3-en yl]-
1
ben zoh yd r a zid e (a n ti-3i): Mp 115-116 °C. H NMR (400
MHz, CDCl3) δ 0.77 (t, J ) 7.3 Hz, 3H), 0.85 (d, J ) 6.8 Hz,
3H), 1.12-1.24 (m, 1H), 1.27-1.40 (m, 1H), 1.71-1.87 (m, 2H),
2.50-2.54 (m, 1H), 4.95-5.02 (m, 2H), 5.48-5.57 (m, 1H),
7.21-7.5 (m, 9H); 13C NMR (400 MHz, CDCl3) δ 14.7, 14.8,
16.5, 36.3, 45.0, 66.6, 115.9, 126.6, 127.9, 128.5, 129.0, 131.5,
132.5, 132.8, 139.5, 140.0, 165.7. IR (KBr) 3324, 1614, 1575,
1496, 1428, 1370, 1313, 1153, 1093, 1071, 1026, 1012, 916
cm-1. Anal. Calcd for C21H25ClN2O: C, 70.67; H, 7.06; N, 7.85.
Found: C, 70.52; H, 7.15; N, 7.81.
N′-(1,2-Dim et h yl-1-n a p h t h a len -2-ylb u t -3-en yl)b en zo-
1
h yd r a zid e (syn -3e): H NMR (300 MHz, CDCl3) δ 1.01 (d, J
) 7.1 Hz, 3H), 1.56 (s, 3H), 2.62 (qd, J ) 7.1 Hz), 4.87-4.93
(m, 2H), 5.56-5.68 (m, 1H), 7.06 (br, 2H), 7.16-7.89 (m, 12H);
13C NMR (300 MHz, CDCl3) δ 14.7, 20.0, 47.1, 65.3, 115.6,
125.3, 125.9, 126.0, 126.2, 126.6, 127.4, 127.9, 128.2, 128.5,
131.5, 132.3, 132.7, 133.1, 139.5, 141.0, 166.4. IR (KBr) 3290,
1637, 1449, 1131 cm-1. HRMS calcd for C23H24N2O (M+)
331.1889. Found 331.1894.
N′-[1-(4-Ch lor op h en yl)-2-m et h yl-1-p r op ylb u t -3-en yl]-
ben zoh yd r a zid e (syn -3i): Mp 141-143 °C. 1H NMR (300
MHz, CDCl3) δ 0.79-0.86 (m, 6H), 1.15-1.44 (m, 2H), 1.66-
1.79 (m, 1H), 1.84-1.95 (m, 1H), 2.52 (qd, J ) 7.0 Hz, 1H),
4.99-5.03 (m, 2H), 5.09 (br, 1H), 5.66-5.78 (m, 1H), 7.13 (br,
1H), 7.18-7.56 (m, 9H); 13C NMR (300 MHz, CDCl3) δ 14.7,
15.7, 16.6, 36.3, 45.2, 67.2, 115.2, 126.6, 128.0, 128.7, 129.1,
131.6, 132.7, 132.9, 139.3, 140.6, 165.8. IR (KBr) 3301, 1740,
1620, 1575, 1550, 1430, 1401, 1373, 1311, 1150, 1067, 1012,
922 cm-1. Anal. Calcd for C21H25ClN2O: C, 70.67; H, 7.06; N,
7.85. Found: C, 70.43; H, 7.23; N, 7.77.
N′-[1,2-Dim et h yl-1-(2-n it r op h en yl)b u t -3-en yl]b en zo-
h yd r a zid e (a n ti-3f): Mp 141-142 °C. 1H NMR (400 MHz,
CDCl3) δ 0.26 (d, J ) 6.8 Hz, 3H), 1.03 (s, 3H), 2.10 (qd, J )
7.1 Hz, 1H), 4.73-4.79 (m, 2H), 5.13 (br, 1H), 5.30 (ddd, J )
7.1, 10.0, 17.1 Hz, 1H), 6.64 (br, 1H), 6.74-7.91 (m, 9H); 13C
NMR (400 MHz, CDCl3) δ 15.6, 17.1, 48.2, 64.8, 118.3, 122.1,
122.3, 126.7, 128.6, 129.2, 131.8, 132.8, 133.5, 138.7, 146.9,
148.4, 167.2. IR (KBr) 3288, 1635, 1529, 1456, 1351, 1315,
1107, 926, 914 cm-1. Anal. Calcd for C19H21N3O3: C, 67.24; H,
6.24; N, 12.38. Found: C, 67.06; H, 6.43; N, 12.32.
N′-[1,2-Dim et h yl-1-(2-n it r op h en yl)b u t -3-en yl]b en zo-
h yd r a zid e (syn -3f): Mp 105-106 °C. 1H NMR (400 MHz,
CDCl3) δ 1.05 (d, J ) 6.8 Hz, 3H), 1.64 (s, 3H), 2.68 (qd, J )
6.8 Hz, 1H), 4.98-5.06 (m, 2H), 5.62 (ddd, J ) 7.8, 10.3, 18.3
Hz, 1H), 7.35-7.61 (m, 8H), 7.87-7.81 (m, 1H), 7.35-7.61 (m,
1H), 8.35-8.36 (m, 1H); 13C NMR (400 MHz, CDCl3) δ 14.7,
19.7, 30.2, 47.0, 65.3, 116.5, 122.0, 122.3, 126.7, 128.6, 128.9,
131.9, 133.5, 138.5, 146.2, 148.2, 167.4. IR (KBr) 3302, 1637,
1304, 909 cm-1. Anal. Calcd for C19H21N3O3: C, 67.24; H, 6.24;
N, 12.38. Found: C, 66.99; H, 6.30; N, 12.42.
N′-(1-Eth yl-2-m eth yl-1-p-tolylbu t-3-en yl)ben zoh yd r a -
1
zid e (a n ti-3j): Mp 111 °C. H NMR (300 MHz, CDCl3) δ 0.87
(t, J ) 7.5 Hz, 3H), 0.89 (d, J ) 6.8 Hz, 3H), 1.85-1.95 (m,
2H), 2.29 (s, 3H), 2.54 (qd, J ) 7.2 Hz, 1H), 4.73 (dd, J ) 1.8,
7.2 Hz, 1H), 5.02 (brd, J ) 17.2 Hz, 1H), 5.51-5.63 (m, 1H),
7.09-7.81 (m, 11H); 13C NMR (300 MHz, CDCl3) δ 7.8, 15.1,
20.9, 26.3, 44.8, 66.8, 115.4, 126.6, 127.6, 128.6, 128.8, 131.5,
133.1, 136.3, 137.7, 140.6, 165.1. IR (KBr) 3298, 3221, 1816,
1637, 1577, 1544, 1449, 1371, 1321, 1190, 1146, 1100, 1054,
1005, 947, 910 cm-1. Anal. Calcd for C21H26N2O: C,78.22; H,
8.13; N, 8.69. Found: C, 78.19; H, 8.31; N, 8.71.
N′-(1-Eth yl-2-m eth yl-1-p-tolylbu t-3-en yl)ben zoh yd r a -
zid e (syn -3j): H NMR (300 MHz, CDCl3) δ 0.59 (d, J ) 7.0
N′-[1-(4-Br om op h en yl)-1,2-d im eth ylbu t-3-en yl]ben zo-
h yd r a zid e (a n ti-3g): Mp 130-131 °C. 1H NMR (300 MHz,
CDCl3) δ 0.70 (d, J ) 7.0 Hz, 3H), 1.40 (s, 3H), 2.51 (qd, J )
7.3 Hz, 1H), 5.17-5.26 (m, 2H), 5.75 (ddd, J ) 7.3, 9.5, 17.1
Hz, 1H), 7.02 (br, 2H), 7.19-7.50 (m, 9H); 13C NMR (300 MHz,
CDCl3) δ 15.7, 16.9, 31.4, 48.2, 64.9, 118.2, 121.2, 126.7, 128.6,
129.1, 131.8, 132.4. IR (KBr) 3390, 3262, 1649, 1432, 1006
cm-1. Anal. Calcd for C19H21BrN2O: C, 61.13; H, 5.67; N, 7.50.
Found: C, 60.88; H, 5.80; N, 7.41.
N′-[1-(4-Br om op h en yl)-1,2-d im eth ylbu t-3-en yl]ben zo-
h yd r a zid e (syn -3 g): 1H NMR (300 MHz, CDCl3) δ 0.96 (d,
J ) 6.8 Hz, 3H), 1.45 (s, 3H), 2.46-2.53 (m, 1H), 4.88-4.96
(m, 2H), 5.60 (ddd, J ) 8.1, 10.5, 18.3 Hz, 1H), 5.56-5.61 (br,
1H), 7.00 (br, 1H), 7.29-7.55 (m, 9H); 13C NMR (300 MHz,
CDCl3) δ 14.7, 20.0, 47.2, 65.0, 115.9, 121.0, 126.7, 128.4, 128.7,
129.1, 131.3, 131.8, 139.2, 142.6, 166.7. IR (KBr) 3499, 3181,
1633, 1452, 1009 cm-1. HRMS calcd for C19H21N2O (M+)
372.0837. Found 372.0831.
1
Hz, 3H), 0.90 (t, J ) 7.3 Hz, 3H), 1.77-1.90 (m, 1H), 1.92-
2.05 (m, 1H), 2.28 (s, 3H), 2.54 (qd, J ) 7.0, 7.5 Hz, 1H), 5.04
(dd, J ) 1.5, 10.0 Hz, 2H), 5.73 (ddd, J ) 1.5, 7.5, 10.0 Hz,
1H), 7.14 (br, 2H), 7.09-7.55 (m, 9H); 13C NMR (300 MHz,
CDCl3) δ 7.9, 15.8, 20.9, 26.1, 44.8, 67.2, 114.9, 126.6, 127.6,
128.6, 128.7, 131.5, 133.1, 136.3, 137.2, 141.2, 165.5. IR (KBr)
3292, 1638, 1308, 1003 cm-1. HRMS calcd for C21H26N2O (M+)
322.2045. Found 322.2059.
N′-(2-Meth yl-1-p r op yl-1-p-tolylbu t-3-en yl)ben zoh yd r a -
1
zid e (a n ti-3k ): Mp 90-91 °C. H NMR (300 MHz, CDCl3) δ
0.80 (t, J ) 7.3 Hz, 3H), 0.88 (d, J ) 6.8 Hz, 3H), 1.21-1.41
(m, 2H), 1.67-1.91 (m, 2H), 2.28 (s, 3H), 2.55 (qd, J ) 7.0 Hz,
1H), 4.96 (dd, J ) 1.7, 10.2 Hz, 1H), 5.02 (brd, J ) 17.2 Hz,
1H), 5.60 (ddd, J ) 8.6, 10.2, 18.5 Hz, 1H), 7.09-7.11 (br, 2H),
7.18-7.54 (m, 9H); 13C NMR (300 MHz, CDCl3) δ 14.9, 15.1,
16.6, 20.9, 36.5, 45.3, 66.7, 115.5, 126.6, 127.4, 128.6, 128.8,
J . Org. Chem, Vol. 67, No. 15, 2002 5363