1116
M. Kokubo et al. / Tetrahedron 66 (2010) 1111–1118
26
J¼6.2 Hz, 1H), 6.52–6.54 (m, 2H), 6.53–6.65 (m, 1H), 7.03–7.06 (m,
2H), 7.20–7.27 (m, 9H); 13C NMR
64.8, 78.0, 114.2, 118.0, 126.6,
found 318.1827; [
a]
þ74.4 (c 1.01, CH2Cl2, 95% ee (1R,2R)); lit.5d
D
24
d
[a
]
ꢁ47.3 (c 0.54, CH2Cl2, 90% ee, (1S,2S)); HPLC (Daicel Chiralpak
D
127.3, 127.5, 127.9, 128.2, 128.6, 129.0, 140.2, 140.6, 147.2; IR (KBr):
3407, 3058, 3028, 1502, 1453, 1317, 1262, 1155, 1051 cmꢁ1; HRMS
ADH, eluent n-hexane/i-PrOH¼19/1, flow rate 1.0 mL/min,
tR¼25.2 min (minor, (1S,2S)); tR¼30.6 min (major, (1R,2R))).
(ESI, Pos.): Calcd for C21H19F3NO [MþH]þ 358.1418, found 358.1457;
26
[
a]
þ42.1 (c 0.99, CH2Cl2, 92% ee); HPLC (Daicel Chiralpak AD,
4.3.1.8. (1R,2R)-2-(Phenylamino)-1,2-di(p-bromophenyl)ethanol
D
eluent n-hexane/i-PrOH¼19/1, flow rate 1.0 mL/min, tR¼15.9 min
(minor); tR¼18.5 min (major)).
(4h). 1H NMR
d
2.58 (br s, 1H), 4.40 (d, J¼6.2 Hz, 1H), 4.52 (br s, 1H),
4.73 (d, J¼6.2 Hz, 1H), 6.48–6.49 (m, 2H), 6.66–6.67 (m, 1H), 7.02–
7.07 (m, 6H), 7.34–7.40 (m, 4H); 13C NMR
64.3, 77.3, 114.2, 118.4,
d
4.3.1.3. (1R,2R)-2-(Naphthalen-1-ylamino)-1,2-diphenylethanol
121.5, 122.0, 128.3, 129.0, 129.1, 131.4, 131.7, 138.9, 139.3, 146.7; IR
(KBr): 3398, 3049, 2363, 2344, 1601, 1501, 1486, 1430, 1403, 1315,
(4c). 1H NMR
d
2.54 (br s, 1H), 4.68 (d, J¼9.6 Hz, 1H), 4.99(d,
J¼9.6 Hz, 1H), 5.51 (br s, 1H), 6.27–6.28 (m, 1H), 7.06–7.41 (m, 14H),
7.72–7.77 (m, 1H), 7.96–7.97 (m, 1H); 13C NMR
64.5, 78.2, 106.7,
1071, 1008, 829, 751, 691 cmꢁ1; HRMS (ESI, Pos.): Calcd for
26
d
C20H18Br2NO [MþH]þ 447.9735, found 447.9763; [
a
]
þ72.0 (c 1.01,
D
117.7, 120.0, 124.0, 124.8, 125.6, 126.3, 126.5, 127.2, 127.5, 128.0,
128.3, 128.6, 128.7, 134.2, 139.9, 140.7, 142.1; IR (KBr): 3406, 3059,
CH2Cl2, 90% ee); HPLC (Daicel Chiralpak AD, eluent n-hexane/
i-PrOH¼19/1, flow rate 1.0 mL/min, tR¼32.3 min (minor, (1S,2S));
tR¼41.5 min (major, (1R,2R))).
3030, 1580, 1523, 1476, 1453, 1407, 1342, 1280, 1032, 768, 700 cmꢁ1
;
HRMS (ESI, Pos.): Calcd for C24H22NO [MþH]þ 340.1701, found
26
22
340.1680; [
a
]
þ126.6 (c 1.07, CH2Cl2, 95% ee (1R,2R)); lit.5d
[a
]
4.3.1.9. (1R,2R)-3-(Phenylamino)-2-butanol (4i). 1H NMR
d 1.14
D
D
ꢁ144.9 (c 0.39, CH2Cl2, 91% ee (1S,2S)); HPLC (Daicel Chiralpak OD,
eluent n-hexane/i-PrOH¼4/1, flow rate 1.0 mL/min (major, (1R,2R)),
tR¼11.4 min; tR¼21.0 min (minor, (1S,2S))).
(d, J¼6.9 Hz, 3H), 1.25 (d, J¼6.9 Hz, 3H), 2.62 (br s, 1H), 3.29–3.34
(m,1H), 3.61–3.65 (m,1H), 6.66–6.74 (m, 3H), 7.15–7.23 (m, 2H); 13C
NMR d 17.3, 19.5, 56.0, 71.3, 114.3, 118.2, 129.3, 147.8; IR (KBr): 3398,
2973, 2929, 1602, 1503, 1318, 1256, 750, 693 cmꢁ1; HRMS (ESI,
Pos.): Calcd for C10H16NO [MþH]þ 166.1232, found 166.1259; [
a]
D
25
4.3.1.4. (1R,2R)-2-(N-Methyl-N-phenylamino)-1,2-diphenyletha-
25
nol (4d). 1H NMR
d
2.70 (s, 3H), 3.95 (br s, 1H), 4.86 (d, J¼9.7 Hz,
1H), 5.27(d, J¼9.7 Hz, 1H), 6.88–6.90 (m, 1H), 6.90–7.00 (m, 4H),
7.11–7.27 (m, 8H), 7.36–7.38 (m, 2H); 13C NMR
32.8, 71.6, 73.6,
ꢁ50.1 (c 0.99, CH2Cl2, 90% ee (1R,2R)); lit.16
[
a]
ꢁ38.3 (c 0.95,
D
benzene, >99.9% ee (1R,2R)); HPLC (Daicel Chiralpak OD, eluent
n-hexane/i-PrOH¼19/1, flow rate 1.0 mL/min, tR¼26.0 min (major
(1R,2R)); tR¼29.9 min (minor (1S,2S))).
d
117.7, 120.3, 127.6, 127.7, 127.8, 128.0, 128.2, 128.8, 129.1, 134.8, 140.7,
151.4; IR (KBr): 3423, 3060, 3030, 1597, 1561, 1451, 1320, 1188, 1079,
1055, 1030, 935, 754, 698 cmꢁ1; HRMS (ESI, Pos.): Calcd for
4.3.1.10. 3-(1-Naphthylamino-1-yl)-2-butanol (4j). 1H NMR
26
C21H22NO [MþH]þ 304.1701, found 304.1739; [
a]
ꢁ171.6 (c 0.99,
d
1.21 (d, J¼6.4 Hz, 3H), 1.28 (d, J¼6.4 Hz, 3H), 2.60 (br s, 1H), 3.49–
3.56 (m, 1H), 3.75–3.82 (m, 1H), 4.24 (br s, 1H), 6.68 (d, J¼7.2 Hz,
1H), 7.20–7.44 (m, 4H), 7.75–7.82 (m, 2H); 13C NMR
17.0,19.8, 55.3,
71.4, 105.9, 117.9, 119.9, 124.0, 124.8, 125.7, 126.5, 128.7, 134.4, 142.6;
D
22
CH2Cl2, 95% ee (1R,2R)); lit.5d
[a
]
þ171.7 (c 0.53, CH2Cl2, 96% ee,
D
(1S,2S)); HPLC (Daicel Chiralpak ASH, eluent n-hexane/i-PrOH¼19/
1, flow rate 0.8 mL/min, tR¼15.2 min (major, (1R,2R)); tR¼21.0 min
(minor, (1S,2S))).
d
IR (KBr): 3424, 2970, 2927, 1580, 1526, 1408, 1121, 1011, 769 cmꢁ1
;
HRMS (ESI, Pos.): Calcd for C14H18NO [MþH]þ 216.1388, found
26
4.3.1.5. (1R,2R)-2-(2-Methoxyphenylamino)-1,2-diphenylethanol
216.1400; [
a
]
D
ꢁ64.6 (c 1.00, CH2Cl2, 67% ee); HPLC (Daicel
(4e). 1H NMR
d
2.66 (br s,1H), 3.85 (s, 3H), 4.50 (d, J¼6.2 Hz,1H), 4.86
(d, J¼6.2 Hz,1H), 5.12 (br s,1H), 6.37–6.39 (m,1H), 6.58–6.74 (m, 3H),
7.14–7.26 (m, 10H); 13C NMR
55.6, 65.0, 78.3,109.7,111.8,117.2,121.1,
Chiralpak AD, eluent n-hexane/i-PrOH¼30/1, flow rate 1.0 mL/min,
tR¼15.0 min (minor); tR¼17.0 min (major)).
d
126.7,127.3,127.8,128.0,128.4,137.1,140.7,147.4; IR (KBr): 3403, 3061,
3027, 1601, 1509, 1454, 1428, 1342, 1224, 1125, 1048, 1026, 768, 738,
4.3.1.11. (1R,2R)-2-Phenylamino-1-cyclohexanol (4k). 1H NMR
d
1.10–1.08 (m, 1H), 1.27–1.43 (m, 3H), 1.40–1.43 (m, 2H), 1.70–1.78
(m, 2H), 3.00 (br s, 1H), 3.11–3.16 (m, 1H), 3.33–3.37 (m, 1H), 6.70–
6.76 (m, 2H), 7.16–7.25 (m, 2H); 13C NMR
24.2, 25.0, 31.5, 33.1,
700 cmꢁ1; HRMS (ESI, Pos.): Calcd for C21H22NO2 [MþH]þ 320.1650,
26
found 320.1665; [
a
]
þ51.9 (c 1.08, CH2Cl2, 95% ee (1R,2R)); lit.5d
d
D
22
[a]
ꢁ48.0 (c 0.54, CH2Cl2, 93% ee, (1S,2S)); HPLC (Daicel Chiralpak
60.2, 74.5,114.4,118.4,129.3,147.7; IR (KBr): 3394, 2924, 2858,1599,
D
ASH, eluent n-hexane/i-PrOH¼19/1, flow rate 0.8 mL/min,
1513, 1497, 1449, 1321, 1052, 864, 741, 689 cmꢁ1; HRMS (ESI, Pos.):
26
tR¼20.4 min (minor, (1S,2S)); tR¼24.9 min (major, (1R,2R))).
Calcd for C12H18NO [MþH]þ 192.1388, found 192.1377; [
a
]
D
ꢁ44.7
25
(c 0.99, CH2Cl2, 90% ee (1R,2R)); lit.17
[
a
]
ꢁ37.7 (c 0.54, CH2Cl2, 54%
D
4.3.1.6. (1R,2R)-2-(Phenylamino)-1,2-di(m-tolyl)-ethanol (4f). 1H
ee (1R,2R)); HPLC (Daicel Chiralpak OD, eluent n-hexane/
i-PrOH¼19/1, flow rate 1.0 mL/min, tR¼18.9 min (minor, (1S,2S));
tR¼22.3 min (major, (1R,2R))).
NMR
4.55 (br s, 1H), 4.85 (d, J¼5.5 Hz, 1H), 6.50–6.52 (m, 2H), 6.60–6.64
(m, 1H), 7.02–7.17 (m, 10H); 13C NMR
21.4, 64.6, 77.9, 114.1, 117.8,
d
2.28 (s, 3H), 2.31 (s, 3H), 2.44 (br s, 1H), 4.48 (d, J¼5.5 Hz, 1H),
d
123.5, 124.3, 127.9, 128.1, 128.3, 128.4, 128.6, 129.0, 137.9, 138.2, 140.3,
140.6, 147.3; IR (KBr): 3406, 3049, 3021, 1602, 1503, 1430, 1317, 1267,
4.3.1.12. 2-(1-Naphthylamino-1-yl)-1-cyclohexanol (4l). 1H NMR
d
1.05–1.10 (m, 1H), 1.29–1.44 (m, 3H), 1.69–1.78 (m, 2H), 2.11–2.23
1155,1048, 789, 749, 706 cmꢁ1; HRMS (ESI, Pos.): Calcd for C22H24NO
(m, 2H), 2.85 (br s, 1H), 3.29–3.36 (m, 1H), 3.46–3.52 (m, 1H), 6.76
27
[MþH]þ 318.1858, found 318.1827; [
a]
D
þ41.3 (c 0.05, CH2Cl2, 95% ee
(d, J¼7.2 Hz, 1H), 7.29–7.44 (m, 4H), 7.72–7.82 (m, 1H); 13C NMR
(1R,2R)); lit.17
[a]
þ50.2 (c 0.89, CH2Cl2, 95% ee (1R,2R)); HPLC
d 24.2, 25.0, 31.5, 33.1, 60.2, 74.5, 114.4, 118.4, 129.3, 147.7; IR (KBr):
23
D
(Daicel Chiralpak OD, eluent n-hexane/i-PrOH¼9/1, flow rate 0.8 mL/
min, tR¼12.1 min (major, (1R,2R)); tR¼15.9 min (minor, (1S,2S))).
3515, 3399, 3049, 2922, 2855, 1576, 1537, 1489, 1446, 1411, 1282,
1064, 766 cmꢁ1; HRMS (ESI, Pos.): Calcd for C16H20NO [MþH]þ
26
242.1545, found 242.1552; [
a
]
ꢁ63.0 (c 0.99, CH2Cl2, 90% ee);
D
4.3.1.7. (1R,2R)-2-(Phenylamino)-1,2-di(p-tolyl)-ethanol (4g). 1H
HPLC (Daicel Chiralpak OD, eluent n-hexane/i-PrOH¼19/1, flow rate
NMR
1H), 4.55 (br s, 1H), 4.81 (d, J¼5.5 Hz, 1H), 6.49–6.51 (m, 2H), 6.60–
6.64 (m, 1H), 7.01–7.22 (m, 10H); 13C NMR
21.1, 64.3, 77.8, 114.1,
d
2.28 (s, 3H), 2.31 (s, 3H), 2.44 (br s, 1H), 4.48 (d, J¼5.5 Hz,
1.0 mL/min, tR¼18.9 min (minor); tR¼22.3 min (major)).
d
4.3.1.13. 2-(N-Methyl-N-phenylamino)-1,2-di(p-tolyl)-ethanol
117.8, 126.5, 127.2, 128.9, 129.0, 129.2, 137.0, 137.3, 137.4, 137.7, 147.7;
IR (KBr): 3398, 3020, 2920, 1602, 1502, 1318, 1048, 819, 749,
691 cmꢁ1; HRMS (ESI, Pos.): Calcd for C22H24NO [MþH]þ 318.1858,
(4m). 1H NMR
d
2.20 (s, 3H), 2.24 (s, 3H), 2.64 (s, 3H), 3.97 (br s,1H),
4.85 (d, J¼10.3 Hz, 1H), 5.23 (d, J¼10.3 Hz, 1H), 6.85–6.93 (m, 5H),
7.00–7.04 (m, 4H), 7.21–7.29 (m, 4H); 13C NMR
21.0, 32.4, 71.1,
d