Organic & Biomolecular Chemistry
Page 6 of 8
20
rate: 0.6 mL•min–1; detection: 254 nm light); tR (major) = 12.56
data: [α]D = –52.4 (c = 1.80, CHCl3) for a product with 90%
min; tR (minor) = 13.89 min. [α]D20 = −9.8° (c = 1.00, CHCl3) for
ee.6 b
(–)-Cyclohexyl(o-tolyl)methanol (4c):25 1H NMR (400 Hz,
a 55% ee sample.
(–)-(3-Bromophenyl)cyclopentylmethanol (1d): 1H NMR 60 CDCl3): δ 7.42 (d, J = 6.0 Hz, 1H), 7.14–7.23 (m, 3H), 4.60 (d, J
5
(500 MHz, CDCl3): δ 7.50 (s, 1H), 7.18–7.40 (m, 3H), 4.38 (d, J
= 8.0 Hz, 1H), 2.10–2.22 (m, 1H), 1.97 (br, 1H), 1.13–1.90 (m,
8H). 13C NMR (125 MHz, CDCl3): δ 147.0, 130.8, 130.1, 129.8,
125.4, 122.7, 78.6, 47.9, 29.6, 29.5, 25.7, 25.6. IR (thin film):
= 7.0 Hz, 1H), 2.35 (s, 3H), 1.98–2.04 (m, 1H), 1.11–1.78 (m,
11H). 13C NMR (100 Hz, CDCl3): δ 142.0, 135.1, 130.3, 127.0,
126.3, 126.1, 75.1, 44.5, 29.6, 28.6, 26.5, 26.3, 26.1, 19.5. IR
(thin film): νmax (cm–1) = 3391, 3023, 1488, 1450, 1051, 756, 729.
νmax (cm–1) = 3409, 2953, 1488, 1435, 1044, 785, 702. MS (EI, 65 MS (EI, m/z, relative intensity): 204 (M+, 5), 121 (100). Chiral
10 m/z, relative intensity): 254 (M+, 5), 256 (M+, 5), 185 (100), 187
(98). HRMS (EI) Calcd for C12H15OBr [M]+: 254.0306, Found:
254.0301. Chiral HPLC, Chiralcel OD-H column (eluent, 2-
propanol/hexane 2:98; flow rate: 0.5 mL•min–1; detection:
254 nm light); tR (major) = 12.88 min; tR (minor) = 16.69 min.
15 [α]D20 = −22.1° (c = 1.00, CHCl3) for a 92% ee sample.
HPLC, Chiralcel OD-H column (eluent, 2-propanol/hexane 3:97;
flow rate: 0.5 mL•min–1; detection: 254 nm light); tR (major) =
15.53 min; tR (minor) = 18.71 min. [α]D20 = −15.5° (c = 0.75,
CHCl3) for a 57% ee sample.
70
(–)-(3-Bromophenyl)cyclohexylmethanol (4d): 1H NMR
(400 Hz, CDCl3): δ 7.19–7.46 (m, 4H), 4.33 (d, J = 7.2 Hz, 1H),
0.91–2.04 (m, 12H). 13C NMR (100 Hz, CDCl3): δ 145.9, 130.4,
129.7, 129.6, 125.3, 122.4, 78.6, 44.9, 29.2, 28.5, 26.3, 26.0, 25.9.
IR (thin film): νmax (cm–1) = 3333, 3061, 1472, 1449, 1023, 783.
(–)-Cyclopentyl(3-methoxyphenyl)methanol (1e):8,12 1H
NMR (500 MHz, CDCl3): δ 6.80–7.24 (m, 4H), 4.37 (d, J = 8.0
Hz, 1H), 3.81 (s, 3H), 2.18–2.20 (m, 1H), 1.12–1.90 (m, 9H). 13
C
NMR (100 MHz, CDCl3): δ 1159.9, 146.4, 129.5, 119.1, 113.2, 75 HRMS (EI) Calcd for C13H17OBr [M]+: 268.0463, Found:
20 112.2, 79.3, 55.4, 47.8, 29.7, 25.7. MS (EI, m/z, relative intensity):
206 (M+, 100). Chiral HPLC, Chiralcel OD-H column (eluent, 2-
propanol/hexane 5:95; flow rate: 1.0 mL•min–1; detection:
254 nm light); tR (major) = 13.30 min; tR (minor) = 15.33 min.
[α]D20 = −27.2° (c = 1.00, CHCl3) for a 91% ee sample.
268.0459. Chiral HPLC, Chiralcel OD-H column (eluent, 2-
propanol/hexane 2:98; flow rate: 0.5 mL•min–1; detection: 254
nm light); tR (major) = 21.10 min; tR (minor) = 30.45 min.
[α]D20 = −13.5° (c = 1.00, CHCl3) for a 94% ee sample.
80
(S)-Cyclohexyl(3-methoxyphenyl)methanol (4e):4b,6b 1H
NMR (400 Hz, CDCl3): δ 7.24–7.28 (m, 1H), 6.81–6.89 (m, 3H),
4.35 (q, J = 3.3 Hz, 1H), 3.83 (s, 3H), 1.97–2.01 (m, 1H), 0.94–
1.85 (m, 11H). 13C NMR (100 Hz, CDCl3): δ 158.5, 144.4, 128.1,
118.0, 111.7, 111.1, 78.3, 54.2, 43.9, 28.3, 27.8, 25.4, 25.1, 24.9.
25
(–)-Cyclopentyl(4-(trifluoromethyl)phenyl)methanol (1f):
1H NMR (400 MHz, CDCl3): δ 7.59 (d, J = 8.2 Hz, 2H), 7.45 (d,
J = 8.2 Hz, 2H), 4.48 (d, J = 8.0 Hz, 1H), 2.05–2.21 (m, 1H),
1.14–1.87 (m, 9H). 13C NMR (100 Hz, CDCl3): δ 148.3, 129.7,
126.7, 125.2, 122.9, 122.8, 78.3, 47.7, 29.3, 29.1, 25.4. IR (thin 85 IR (thin film): νmax (cm–1) = 3429, 2999, 1487, 1452, 1046, 784,
30 film): νmax (cm–1) = 3392, 2958, 1454, 1453, 1017, 838. HRMS
(EI) Calcd for C13H15OF3 [M]+: 244.1075, Found: 244.1080.
Chiral HPLC, Chiralcel AD column (eluent, 2-propanol/hexane
5:95; flow rate: 0.5 mL•min–1; detection: 254 nm light); tR (minor)
= 13.55 min; tR (major) = 14.62 min. [α]D20 = −27.5° (c = 1.00,
35 CHCl3) for a 91% ee sample.
703. MS (EI, m/z, relative intensity): 220 (M+, 11), 137 (100).
Chiral HPLC, Chiralcel OD-H column (eluent, 2-
propanol/hexane 5:95; flow rate: 0.7 mL•min–1; detection: 254
nm light); tR (S) = 16.05 min; tR (R) = 27.34 min.
90
(–)-Cyclohexyl(4-(trifluoromethyl)phenyl)methanol (4f):6b
1H NMR (400 Hz, CDCl3): δ 7.58 (d, J = 8.0 Hz, 2H), 7.40 (d,
J = 8.0 Hz, 2H), 4.44 (d, J = 6.8 Hz, 1H), 2.06 (m, 1H), 0.99–1.90
(m, 11H). 13C NMR (100 Hz, CDCl3): δ 147.5, 126.9, 125.1,
122.9, 78.7, 45.0, 29.2, 28.4, 26.3, 26.0. IR (thin film): νmax (cm–1)
(–)-Cyclopentyl(p-tolyl)methanol (1g):26 1H NMR (500 MHz,
CDCl3): δ 7.24 (d, J = 10.0 Hz, 2H), 7.15 (d, J = 10.0 Hz, 2H),
4.36 (d, J = 10.5 Hz, 1H), 2.34 (s, 3H), 2.21–2.23 (m, 1H), 1.11–
1.82 (m, 10H). 13C NMR (100 Hz, CDCl3): δ 141.5, 137.2, 129.0, 95 = 3366, 2929, 1451, 1418, 1068, 761.MS (EI, m/z, relative
40 126.4, 79.0, 47.6, 29.6, 29.5, 25.6, 25.4, 21.1. IR (thin film): νmax
(cm–1) = 3418, 2955, 1455, 1030, 816, 741. MS (EI, m/z, relative
intensity): 190 (M+, 56), 121 (100). Chiral HPLC, Chiralcel OB-
intensity): 258 (M+, 2), 175 (100). Chiral HPLC, Chiralcel OD-H
column (eluent, 2-propanol/hexane 2:98; flow rate: 0.3 mL•min–1;
detection: 254 nm light); tR (major) = 27.65 min; tR (minor) =
30.25 min. [α]D20 = −21.8° (c = 1.00, CHCl3) for a 95% ee sample.
H
column (eluent, 2-propanol/hexane 2:98; flow rate:
0.5 mL•min–1; detection: 254 nm light); tR (major) = 15.62 min;
45 tR (minor) = 18.03 min. [α]D20= −31.4° (c = 1.00, CHCl3) for a
93% ee sample.
100
(–)-Cyclohexyl(p-tolyl)methanol (4g):27 1H NMR (500 Hz,
CDCl3): δ 7.15–7.21 (m, 4H), 4.33 (d, J = 7.5 Hz, 1H), 2.35 (s, 3
H), 0.90–2.02 (m, 12H). 13C NMR (100 Hz, CDCl3): δ 140.7,
136.9, 128.8, 126.6, 79.2, 44.9, 29.3, 28.9, 26.5, 26.1, 26.0, 21.1.
IR (thin film): νmax (cm–1) = 3391, 3021, 1450, 1017, 821. MS (EI,
(–)-(2-Chlorophenyl)cyclohexylmethanol (4b):6b 1H NMR
(400 Hz, CDCl3): δ 7.18–7.51 (m, 4H), 4.91–4.94 (m, 1H), 1.10–
1.93 (m, 12H). 13C NMR (100 Hz, CDCl3): δ 140.1, 131.5, 128.3, 105 m/z, relative intensity): 204 (M+, 4), 121 (100). Chiral HPLC,
50 127.2, 125.8, 73.9, 42.9, 28.4, 26.8, 25.4, 25.3, 25.0. IR (thin
film): νmax (cm–1) = 3373, 3071, 1472, 1449, 1035, 755, 700.
MS (EI, m/z, relative intensity): 222 ([M–H]+, 16), 141 (30), 139
(100). Chiral HPLC, Chiralcel OD-H column (eluent, 2-
propanol/hexane 2:98; flow rate: 0.5 mL•min–1; detection: 254
55 nm light); tR (major) = 15.56 min; tR (minor) = 18.28 min.
[α]D20 = −22.0° (c = 1.00, CHCl3) for a 72% ee sample. Literature
Chiralcel OD-H column (eluent, 2-propanol/hexane 3:97; flow
rate: 0.5 mL•min–1; detection: 254 nm light); tR (major) = 24.87
min; tR (minor) = 31.56 min. [α]D20 = −29.7° (c = 1.00, CHCl3)
for a 95% ee sample.
110
(–)-Cyclohexyl(4-(phenyl)phenyl)methanol (4h):28 1H NMR
(400 Hz, CDCl3): δ 7.55–7.61 (m, 4H), 7.31–7.46 (m, 5H), 4.42
6
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]