H. Naeimi, M. Moradian / Tetrahedron: Asymmetry 25 (2014) 429–434
433
Anal. Calcd for C32H30N2S2: C, 75.85; H, 5.97; N, 5.53; S, 12.66.
Found: C, 75.92, H, 5.90; N, 5.48; S, 12.55.
J = 8.4 Hz, 2H), 7.32 (m, 3H), 7.45 (m, 2H), 7.50 (m, 2H). 13C NMR
(CDCl3, 100 MHz): 44.11, 49.25, 61.48, 68.03, 85.15, 88.54,
113.85, 120.41, 123.74, 128.19, 130.04, 131.21, 134.30, 152.71.
MS: 320 ([M+1]+, 2.7), 215 (M+, 11), 276 (38), 234 (22), 219 (38),
4.8.4. (1R,2R)-N,N-Bis[2-(phenylthio)benzylidene]-1,2-diamin
ocyclohexane triphenyl phosphine copper(I) bromide 3e
IR (neat, thin film): 3062 (m), 2941 (w), 1608 (m), 1504 (s),
1454 (m), 1442 (m), 1247 (s), 1240 (m) 1124 (m), 1038 (m), 843
101 (10), 86 (100), 76 (100); ½a D20
¼ þ30:7 (c 0.85, CDCl3); 54% ee
ꢀ
as a light red oil; Rf = 0.80 (EtOAc/petroleum ether = 2:8); HPLC
conditions: Diacel chiralcel OD-H (4.6 cm I.D. ꢁ 25 cm), 98:2 hex-
(s), 739 (m), 682 (s), 502 (m), 462 (m) and 431 (m) cmꢂ1
;
1H
ane/n-PrOH, 500 lL/min flow rate, k = 254 nm, TR (minor) = 13.27 -
NMR (CDCl3, 400 MHz): d 9.28 (2H, s), 8.17 (2H, d, J = 6.6 Hz),
7.24–7.38 (15H, m), 7.16–7.24 (16H, m), 3.14–3.19 (2H, m);
1.84–1.97 (8H, m); MS (EI) m/z (%): 910 (M+, 3.54), 262 (100).
min and TR (major) = 14.98 min.
4.9.6. 4-(1-(3-Methoxyphenyl)-3-phenylprop-2-yn-1-yl)
morpholine 7f
4.9. Characterization data of propargylamines 7a–n
IR (thin film): 3057, 2995, 2851, 1965, 1599, 1486, 1449, 1314,
1256, 1314, 1256, 1150, 1115, 1044, 1001, 867, 758, 692, 564. 1H
NMR (CDCl3, 400 MHz): 2.66 (m, 4H), 3.77 (m, 4H), 3.85 (s, 3H),
4.79 (s, 1H), 6.87 (d, 8.3 Hz, 1H), 7.25–7.36 (m, 6H), 7.53 (m, 2H).
13C NMR (CDCl3, 100 MHz): 49.99, 55.24, 62.01, 67.20, 85.15,
88.54, 113.10, 114.39, 120.99, 123.03, 128.36, 128.42, 129.28,
4.9.1. 4-(1,3-Diphenylprop-2-yn-1-yl)morpholine 7a
red oil; IR (thin film): 3059, 3029, 2957, 2853, 2820, 2221, 1598,
1489, 1449, 1318, 1280, 1114, 1001, 865, 758, 694, 562, 526 cmꢂ1
;
1H NMR (CDCl3, 400 MHz): 2.68 (m, 4H), 3.78 (m, 4H), 4.84 (s, 1H),
7.33–7.44 (m, 6H), 7.56–7.58 (m, 2H), 7.69 (m, 2H) ppm; 13C NMR
(CDCl3, 100 MHz): 54.3, 55.2, 68.7, 86.2, 88.4, 115.1, 116.3, 121.9,
123.0, 124.2, 126.6, 130.4, 135.8, 137.0, 140.5, 160.7 ppm;
131.88, 132.17, 139.57, 159.71 ppm; ½a D20
¼ þ58:0 (c 1.5, CDCl3);
ꢀ
57% ee as
a light orange oil; Rf = 0.50 (EtOAc/petroleum
ether = 2:8); HPLC conditions: Diacel chiralcel OD-H (4.6 cm
L/min flow rate,
½
a 2D0
ꢀ
¼ þ50:3 (c 1.35, CDCl3); 44% ee as a light yellow oil;
I.D. ꢁ 25 cm), 98:2 hexane/n-PrOH, 500
l
Rf = 0.60 (EtOAc/petroleum ether = 2:8); HPLC conditions: Diacel
k = 254 nm, TR (minor) = 12.07 min and TR (major) = 14.41 min.
chiralcel OD-H (4.6 cm I.D. ꢁ 25 cm), 98:2 hexane/n-PrOH,
500
l
L/min flow rate, k = 254 nm, TR (minor) = 13.27 min and TR
4.9.7. 4-(1-(4-Isopropylphenyl)-3-phenylprop-2-yn-1-yl) mor
pholine 7g
(major) = 15.65 min.
colorless oil; IR (thin film): 3069, 2971, 2936, 2873, 1980, 1430,
4.9.2. 4-(3-Phenyl-1-(p-tolyl)prop-2-yn-1-yl)morpholine 7b
1326, 1128, 1011, 859, 783, 690, 606, 568, 472 cmꢂ1 1H NMR
;
red oil; IR (thin film): 3024, 2964, 2925, 2862, 2820, 1486, 1446,
(CDCl3, 400 MHz): 1.32 (m, 6H), 2.60 (m, 4H), 2.86 (m, 1H), 3.80
(m, 4H), 4.92 (s, 1H), 7.16–7.24 (m, 2H), 7.38–7.51 (m, 3H), 7.70–
7.83 (m, 2H).
1314, 1109, 999, 854, 757, 687, 562, 525, 473 cmꢂ1 1H NMR
;
(CDCl3, 400 MHz): 2.39 (s, 3H), 2.65 (s, 4H), 3.75 (s, 4H), 4.78 (s,
1H), 7.20–7.22 (m, 2H), 7.34–7.36 (m, 3H), 7.53–7.55 (m, 2H);
½
a 2D0
ꢀ
¼ þ37:2 (c 1.10, CDCl3); 43% ee as a light yellow oil;
4.9.8. 4-(1-(2-Chlorophenyl)-3-phenylprop-2-yn-1-yl)mor-
pholine 7h
Rf = 0.60 (EtOAc/petroleum ether = 2:8); HPLC conditions: Diacel
chiralcel OD-H (4.6 cm I.D. ꢁ 25 cm), 98:2 hexane/n-PrOH,
IR (thin film): 3047, 2997, 2897, 2750, 1562, 1472, 1452, 1324,
1274, 1321, 1232, 1145, 1117, 1055, 1008, 888, 765, 627, 520. 1H
NMR (CDCl3, 400 MHz): 2.69 (m, 4H), 3.71 (m, 4H), 5.14 (s, 1H),
7.25–7.30 (m, 2H), 7.33–7.36 (m, 3H), 7.41–7.43 (m, 1H), 7.50–
7.52 (m, 2H), 7.75–7.77 (m, 1H) ppm; 13C NMR (CDCl3,
100 MHz): 49.87, 58.96, 67.14, 84.70, 88.40, 122.82, 125.58,
126.39, 128.38, 128.41, 129.18, 129.94, 130.58, 130.93, 131.85,
500 lL/min flow rate, k = 254 nm, TR (minor) = 10.34 min and TR
(major) = 12.32 min.
4.9.3. 4-(1-(4-Nitrophenyl)-3-phenylprop-2-yn-1-yl)morpholine
7c
IR (thin film): 3067, 2958, 2854, 2216, 1690, 1600, 1522, 1450,
1347, 1275, 1113, 1006, 864, 819, 757, 695, 539. 1H NMR (CDCl3,
400 MHz): 2.63–2.66 (m, 4H), 3.76 (m, 4H), 4.89 (s, 1H), 7.38 (s,
3H), 7.53 (m, 2H), 7.88 (m, 2H), 8.24 (m, 2H). 13C NMR (CDCl3,
100 MHz): 49.90, 61.45, 67.04, 83.16, 89.78, 122.31, 123.48,
134.69, 135.56, 135.82 ppm; ½a D20
¼ þ54:8 (c 2.0, CDCl3); 69% ee
ꢀ
as an orange oil; Rf = 0.70 (EtOAc/petroleum ether = 2:8); HPLC
conditions: Diacel chiralcel OD-H (4.6 cm I.D. ꢁ 25 cm), 98:2
hexane/n-PrOH, 500 lL/min flow rate, k = 254 nm, TR (minor) =
128.45, 128.72, 129.33, 131.85, 145.45 ppm;
0.85, CDCl3); 58% ee as a light yellow oil; Rf = 0.60 (EtOAc/petro-
½
a 2D0
ꢀ
¼ ꢂ28:3 (c
10.77 min and TR (major) = 12.91 min.
leum ether = 2:8); HPLC conditions: Diacel chiralcel OD-H (4.6 cm
4.9.9. 4-(1-(4-Chlorophenyl)-3-phenylprop-2-yn-1-yl)morpho-
line 7i
I.D. ꢁ 25 cm), 98:2 hexane/n-PrOH, 500
lL/min flow rate,
k = 254 nm, TR (minor) = 12.47 min and TR (major) = 14.65 min.
IR (thin film): 3063, 3028, 2956, 2932, 1494, 1454, 1028, 746,
698 cmꢂ1 1H NMR (CDCl3, 400 MHz): 2.62 (m, 4H), 3.73 (m, 4H),
.
4.9.4. 4-(1-(4-Methoxyphenyl)-3-phenylprop-2-yn-1-yl)mor-
pholine 7d
4.77 (s, 1H), 7.36–7.45 (m, 5H), 7.52 (m, 2H), 7.58–7.60 (m, 2H)
ppm; 13C NMR (CDCl3, 100 MHz): 49.85, 61.40, 67.15, 84.43,
88.98, 122.77, 125.59, 128.08, 128.43, 128.48, 129.70, 129.94,
IR (thin film): 3034, 2987, 2888, 1976, 1584, 1469, 1453, 1329,
1243, 1128, 1105, 1061, 1008, 854, 738, 664, 593. 1H NMR (CDCl3,
400 MHz): 2.59 (m, 4H), 3.45 (m, 4H), 3.70 (s, 3H), 4.83 (s, 1H), 6.79
(d, 8.3 Hz, 1H), 7.18–7.27 (m, 6H), 7.47 (m, 2H). 13C NMR (CDCl3,
100 MHz): 51.04, 53.68, 62.24, 68.61, 84.26, 87.08, 111.42,
112.66, 118.26, 121.07, 126.18, 127.25, 128.19, 130.48, 132.70,
140.04, 162.69.
131.57,
¼ þ74:6 (c 2.0, CDCl3); 43% ee as a yellow oil; Rf = 0.60
(EtOAc/petroleum ether = 2:8); HPLC conditions: Diacel chiralcel
OD-H (4.6 cm I.D. ꢁ 25 cm), 98:2 hexane/n-PrOH, 500 L/min flow
rate, k = 254 nm, TR (minor) = 13.62 min and TR
(major) = 15.84 min.
131.88,
132.16,
133.61,
135.86,
136.53 ppm;
½ ꢀ
a 2D0
l
4.9.5. N,N-Dimethyl-4-(1-morpholino-3-phenylprop-2-yn-1-yl)
aniline 7e
4.9.10. 4-(1-(3-Nitrophenyl)-3-phenylprop-2-yn-1-yl)morpho-
line 7j
IR (thin film): 2955, 2892, 2854, 2815, 1965, 1611, 1521, 115,
757, 692, 556. 1H NMR (CDCl3, 400 MHz): 2.65 (m, 4H, H2C-17,
H2C-21), 2.97 (s, 6H), 3.73 (m, 4H), 4.70 (s, 1H), 6.72 (d,
IR (thin film): 3070, 3029, 2957, 2859, 1494, 1454, 1428, 1113,
1075, 739, 711, 703, 672, 534 cmꢂ1 1H NMR (CDCl3, 400 MHz):
.
2.67 (m, 4H), 3.76 (m, 4H), 4.90 (s, 1H), 7.38–7.41 (m, 3H), 7.56–