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A. R. Chaudhary et al. / Tetrahedron: Asymmetry 25 (2014) 767–774
126.5, 126.6, 127.8, 128.0, 128.2, 128.4, 129.3, 129.6, 133.2, 142.1,
143.5, 154.7. EIMS (m/z): 380.95 ([M]+, 42%), 365.91 (11.6%),
303.81 (8%), 275.87 (12%), 246.75 (100%), 214.76 (13%), 104.88
(6%), 90.87 (11%). HRMS: 382.5242 (calcd, M+H). Found: 382.2165.
146.4, 153.4. EIMS (m/z): 395.23 ([M]+, 11%), 318.31 (27%),
317.43 (24%), 290.65 (96%), 289.4 (100%), 247.44 (24%). HRMS:
396.5510 (calcd, M+H). Found: 396.2328.
4.1.8. [(2-Butoxynaphthalen-1-yl)phenylmethyl](1-phenylethyl)-
amine (S,S)-10
4.1.3. 1-Phenyl-2-(1-phenyl-ethyl)-2,3-dihydro-1H-naphtho[1,2-
e][1,3]oxazine (S,S)-6
The procedure was the same as for (S,S)-11. Mp 126–128 °C,
White solid, 90% yield, mp 124–126 °C (reported mp 125–
[
a
]
25 = À45.6 (c 1.0, CHCl3). IR (KBr):
m 3339, 3056, 3026, 2961,
D
128 °C).4b
2874, 1622, 1596, 1515, 1492, 1460, 1447, 1368, 1351, 1252,
1240, 1171, 1148, 1119, 1083, 1068, 1025, 960, 880, 805, 768,
4.1.4. 1-{[Methyl(1-phenylethyl)amino]phenylmethyl}naphtha-
748, 715, 704 cmÀ1 1H NMR (400 MHz, CDCl3): d 0.84–0.88 (m,
.
len-2-ol (S,S)-7
3H), 1.18–1.28 (m, 5H), 1.43–1.5 (m, 2H), 2.30 (br s, 1H), 3.60–
3.65 (q, J = 6.4 Hz, 1H), 3.72–3.78 (q, J = 6.4 Hz, 1H), 4.04–4.09 (q,
J = 6.8 Hz, 1H), 5.62 (s, 1H), 7.12–7.44 (m, 13H), 7.64–7.85 (m,
3H). 13C NMR (100 MHz, CDCl3): d 13.8, 19.1, 25.9, 31.4, 55.1,
55.6, 68.7, 114.6, 123.3, 125.0, 125.7, 126.3, 126.7, 126.7, 127.2,
127.7, 128.2, 128.6, 129.0, 145.3, 146.3, 155.0. EIMS (m/z):
409.59 ([M]+, 16%), 331.37 (24%), 303.53 (100%), 288.22 (11%),
105.15 (9%). HRMS: 410.5778 (calcd, M+H). Found: 410.2478.
White solid, 99% yield, mp 126–128 °C (reported mp 128–
129 °C).4c
4.1.5. [(2-Methoxynaphthalen-1-yl)phenylmethyl](1-phenylethyl)
amine (S,S)-8
Powdered NaOH (0.16 g, 3.95 mmol) was added to a solution of
(S,S)-4 (0.2 g, 0.56 mmol) in THFÁH2O (1:1, 6 mL). After 10 min,
Me2SO4 (0.27 mL, 2.82 mmol) was added to the slurry. The reaction
mixture was then heated at 70 °C for 2 days, after which the reac-
tion mixture was quenched with water and extracted with ethyl-
acetate (2 Â 25 mL). The combined organic layer was washed
with water, the combined organic extracts were dried over anhy-
drous Na2SO4 and the solvent was removed under reduced pres-
sure. The crude product was purified by column chromatography
on silica gel with hexane/EtOAc (10:1) as eluent to give a pale yel-
low solid (0.125 g, 60% yield), mp 102–104 °C (reported mp 104–
106 °C).10b
4.1.9. {[2-(4-Bromobenzyloxy)naphthalen-1-yl]phenylmethyl}-
(1-phenylethyl)amine (S,S)-12
The procedure was the same as for (S,S)-11. Oil, [
1.38, CHCl3). IR (neat): 3349, 3059, 3025, 2959, 1652, 1622, 1596,
1514, 1489, 1456, 1433, 1368, 1351, 1217, 1170, 1147, 1121, 1069,
1012, 960, 880, 841, 805, 760, 701 cmÀ1 1H NMR (400 MHz,
a]
25 = +44.2 (c
D
m
.
CDCl3): d 1.22–1.23 (d, J = 6.8 Hz, 1H), 3.60–3.65 (q, J = 6.4 Hz,
1H), 4.79–4.82 (d, J = 11.6 Hz, 1H), 5.02–5.05 (d, J = 12 Hz, 1H),
5.64 (s, 1H), 6.80–6.82 (d, J = 8 Hz, 2H), 7.16–7.26 (m, 5H), 7.29–
7.43 (m, 10H), 7.68–7.85 (m, 3H). 13C NMR (100 MHz, CDCl3): d
26.0, 55.0, 55.7, 70.2, 114.7, 121.7, 123.7, 125.91, 126.6, 126.8,
127.2, 127.9, 128.3, 128.6, 129.0, 129.2, 131.5, 135.7, 154.2. EIMS
(m/z): 523.48 ([M+1]+, 16%), 522 ([M]+, 18%), 521 (22%), 446.07
(46%), 418.36 (100%), 414.93 (92%), 402.71 (85%), 351.97 (66%),
104.84 (70%). HRMS: 523.4911 (calcd, M+H). Found: 523.1464.
4.1.6. [(2-Benzyloxynaphthalen-1-yl)phenylmethyl](1-phenyl-
ethyl)amine (S,S)-11
To a solution of (S,S)-4 (0.1 g, 0.28 mmol), K2CO3 (0.06 g,
0.42 mmol), and 18-crown-6 (0.015 g, 0.056 mmol) in acetonitrile
(7 mL) was added benzyl chloride (0.072 g, 0.42 mmol). The reac-
tion mixture was heated at 75 °C for 24 h. Then the reaction mix-
ture was quenched with water and extracted with ethylacetate
(2 Â 25 mL). The combined organic layer was washed with water,
dried over Na2SO4, and then concentrated under reduced pressure.
The residue was submitted to chromatographic separation on silica
gel with hexane/EtOAc (20:1) as eluent to give a white solid
4.1.10. {[2-(3,5-Dibromobenzyloxy)naphthalen-1-yl]phenyl-
methyl}(1-phenylethyl)amine (S,S)-13
The procedure was the same as for (S,S)-11. Mp 104–106 °C,
[a] m 3344, 3080, 3060, 3022,
25 = +66.1 (c 1.0, CHCl3). IR (KBr):
D
2956, 1622, 1556, 1513, 1491, 1456, 1425, 1367, 1349, 1282,
1245, 1218, 1200, 1168, 1107, 1088, 1068, 1027, 957, 880, 848,
795, 742, 720, 698, 676, 548, 511 cmÀ1. 1H NMR (400 MHz, CDCl3):
d 1.24–1.26 (d, J = 6.4 Hz, 3H), 2.77 (br s, 1H), 3.60–3.64 (q,
J = 6.4 Hz, 1H), 4.68–4.71 (d, J = 12 Hz, 1H), 4.98–5.01 (d,
J = 12.4 Hz, 1H), 5.66 (s, 1H), 7.11–7.43 (m, 15H), 7.59–7.6 (t, 1H),
7.71 (br s, 1H), 7.84–7.87 (m, 2H). 13C NMR (100 MHz, CDCl3): d
26.0, 54.9, 55.7, 69.7, 114.9, 123.0, 123.7, 124.0, 126.1, 126.4,
126.6, 126.7, 126.9, 127.2, 128.0, 128.3, 128.7, 128.9, 129.3,
129.6, 133.6, 140.7, 144.9, 146.1, 154.0. HRMS: 602.3872 (calcd,
M+H). Found: 602.0509.
(0.107 g, 86% yield). mp 116–118 °C, [
IR (KBr):
a]
D
25 = À68.56 (c 1.0, CHCl3).
m
3348, 3056, 3028, 2968, 2871, 1684, 1623, 1595, 1511,
1492, 1455, 1368, 1352, 1236, 1168, 1123, 1067, 1027, 964, 880,
804, 768, 745, 697 cmÀ1 1H NMR (400 MHz, CDCl3): d 1.25–1.26
.
(d, J = 6.8 Hz, 3H), 3.65–3.70 (q, J = 6.4 Hz, 1H), 4.90–4.93 (d,
J = 12 Hz, 1H), 5.12–5.13 (d, J = 11.6 Hz, 1H), 5.71 (s, 1H), 7.05–
7.06 (m, 2H), 7.18–7.47 (m, 16H), 7.71–7.87 (m, 3H). 13C NMR
(100 MHz, CDCl3): d 25.9, 55.1, 55.7, 71.0, 114.9, 123.6, 125.6,
125.9, 126.5, 126.8, 126.8, 127.2, 127.3, 127.8, 128.3, 128.5,
128.6, 129.1, 136.8, 145.1, 146.3, 154.6. EIMS (m/z): 442.83 ([M]+,
9%), 440.89 (100%), 338.15 (16%). HRMS: 444.5950 (calcd, M+H).
Found: 444.2332.
4.1.11. {[2-(4-Fluorobenzyloxy)naphthalen-1-yl]phenylmethyl}-
(1-phenylethyl)amine (S,S)-14
4.1.7. [(2-Isopropoxynaphthalen-1-yl)phenylmethyl](1-phenyl-
ethyl)amine (S,S)-9
The procedure was the same as for (S,S)-11. Mp 78–80 °C,
[a]
25 = +61.3 (c 1.0, CHCl3). IR (KBr):
m
3344, 3056, 2960, 1623,
1596, 1513, 1492, 1461, 1445, 1368, 1352, 1228, 1156, 1119,
1078, 1067, 1019, 960, 880, 861, 828, 804, 763, 705, 704 cmÀ1
D
The procedure was the same as for (S,S)-11. Mp 128–130 °C,
[
a
]
25 = À71.1 (c 1.0, CHCl3). IR (KBr):
m
3343, 3056, 3027, 2984,
.
D
2952, 1620, 1596, 1512, 1493, 1463, 1448, 1332, 1249, 1234,
1H NMR (400 MHz, CDCl3): d 1.22–1.23 (d, J = 6.4 Hz, 3H), 3.61–
3.66 (q, J = 6.4 Hz, 1H), 4.81–4.84 (d, J = 11.6 Hz, 1H), 5.04–5.07
(d, J = 11.2 Hz, 1H), 5.67 (s, 1H), 6.9–6.97 (m, 4H), 7.18–7.43 (m,
13H), 7.84–7.86 (d, J = 9.2 Hz, 2H). 13C NMR (100 MHz, CDCl3): d
25.9, 55.0, 55.7, 70.4, 114.9, 115.2, 115.4, 123.7, 125.7, 125.9,
126.5, 126.8, 127.2, 127.9, 128.3, 128.7, 129.2, 129.3, 132.5,
132.5, 145.1, 146.2, 154.4, 161.2, 163.6. EIMS (m/z): 460.27 (6%),
441.55 (7%), 356.15 (32%), 355.15 (17%), 339.62 (18%), 232.34
1111, 1060, 1031, 981, 880, 827, 810, 771, 746, 716, 704 cmÀ1
.
1H NMR (400 MHz, CDCl3): d 0.82 (br s, 3H), 1.28–1.30 (d,
J = 6.8 Hz, 6H), 3.06 (br s, 1H), 3.64–3.70 (q, J = 6.4 Hz, 1H), 4.60–
4.70 (h, 1H), 5.60 (s, 1H), 7.16–7.44 (m, 13H), 7.61–7.63 (d,
J = 8 Hz, 1H), 7.81–7.84 (m, 2H). 13C NMR (100 MHz, CDCl3): d
21.3, 22.5, 26.00, 55.0, 55.7, 69.9, 115.1, 123.2, 125.6, 125.8,
126.4, 126.8, 126.8, 127.3, 127.6, 128.2, 128.5, 128.8, 145.5,