T. Yıldız, A. Yusufog˘lu / Tetrahedron: Asymmetry 22 (2011) 1347–1352
1351
1H, J = 6.8 Hz), 6.80 (dd, 2H, J1 = 1.9, J2 = 6.8 Hz), 7.16 (dd, 2H,
4.3.14. (R)-1-(Naphthlalen-2-yl)-1-tridecanol 4r
J1 = 1.9, J2 = 6.8 Hz). 13C NMR (CDCl3): d 14.40, 23.01, 26.20,
29.40–30.01, 32.20, 39.05, 55.03, 75.00, 114.01, 115.09, 125.54,
139.19, 159.20. MS m/z: 43, 44, 69, 94, 121, 137, 147, 320 (M+),
321. Anal. Calcd for C21H36O2: C, 78.70; H, 11.32. Found: C,
78.16; H, 10.97.
Mp 26–27 °C, ½a 2D5
¼ þ52:1 (c 1.1, CHCl3), ee = >99%. HPLC anal-
ꢂ
ysis: Chiralcel OD chiral column, mobile phase iso-PrOH/hexane:
10/90, flow rate: 1.0 mL/min, wavelength: 210 nm; tR (retention
time): not observed (for racemic 6.112 min) for the (S)-isomer,
10.069 min for the (R)-isomer. IR (neat, cmꢁ1): 3346, 3023, 2923,
2853, 1607, 1476, 1276, 1153, 1107, 1046, 846, 753 cmꢁ1 1H
.
NMR (CDCl3): d 0.80 (t, 3H, J = 6.3 Hz), 1.14–1.54 (m, 21H), 1.70–
1.92 (m, 2H), 4.75 (t, 1H, J = 6.8 Hz), 7.40–8.20 (m, 7H). 13C NMR
(CDCl3): d 14.40, 23.10, 26.60, 29.80–30.01, 32.20, 38.80, 72.00,
123.00, 123.40, 125.10, 125.20, 126.20, 128.20, 129.20, 130.10,
134.10, 149.02. MS m/z: 43, 57, 77, 97, 115, 157, 181, 193, 221,
308, 326 (M+). Anal. Calcd for C23H34O: C, 84.60; H, 10.50. Found:
C, 84.52; H, 10.23.
4.3.10. (R)-1-(p-Bromophenyl)-1-tetradecanol 4k
Mp 42.7–43.1 °C, ½a D25
¼ þ13:9 (c 1.1, CHCl3), ee = 92%. HPLC
ꢂ
analysis: Chiralcel OD chiral column, mobile phase iso-PrOH/hex-
ane: 2/98, flow rate: 1.0 mL/min, wavelength: 210 nm; tR (retention
time): 10.521 min for the (R)-isomer, 10.994 min for the (S)-isomer.
IR (neat, cmꢁ1): 3353, 3069, 2923, 2846, 1600, 1476, 1353, 1223,
1130, 1076, 823, 723 cmꢁ1 1H NMR (CDCl3): d 0.80 (t, 3H,
.
J = 6.8 Hz), 1.12–1.34 (m, 22H), 1.54–1.72 (m, 2H), 1.80 (br s, 1H),
4.53 (t, 1H, J = 7.3 Hz), 7.14 (dd, 2H, J1 = 1.9, J2 = 6.3 Hz), 7.39 (dd,
2H, J1 = 1.9, J2 = 6.3 Hz). 13C NMR (CDCl3): d 14.50, 23.50, 26.20,
29.80–30.01, 32.20, 39.40, 74.00, 121.01, 127.90, 131.80, 144.19.
MS m/z: 43, 55, 77, 106, 120, 157, 185, 368, 369 (M+). Anal. Calcd
for C20H33BrO: C, 65.03; H, 9.00. Found: C, 65.41; H, 9.09.
4.3.15. (R)-(4-t-Butylphenyl)(phenyl)methanol 4s
Mp 79.7–80.5 °C, ½a D25
¼ þ52:9 (c 1.1, CHCl3), ee = 90%. HPLC
ꢂ
analysis: Chiralcel OD chiral column, mobile phase iso-PrOH/
hexane: 10/90, flow rate: 1.0 mL/min, wavelength: 210 nm; tR
(retention time): 8.807 min for the (S)-isomer, 9.884 min for the
(R)-isomer. IR (neat, cmꢁ1): 3229, 3030, 2959, 2855, 1599, 1449,
1339, 1270, 1110, 1011, 755, 630 cmꢁ1 1H NMR (CDCl3): d 1.12
.
4.3.11. (R)-1-(p-Hydroxyphenyl)-1-tetradecanol 4m
(s, 9H), 2.20 (br s, 1H), 5.70 (s, 1H), 7.10–7.40 (m, 9H). 13C NMR
(CDCl3): d 32.14, 34.35, 76.04, 125.20, 126.50, 126.70, 127.50,
128.50, 141.00, 144.19, 150.80. MS m/z: 41, 51, 77, 91, 105, 119,
134, 183, 209, 225, 240 (M+). Anal. Calcd for C17H20O: C, 84.96;
H, 8.39. Found: C, 85.15; H, 8.12.
Mp 66.2–67.1 °C, ½a D25
¼ þ4:6 (c 1.1, CHCl3), ee = 22%. HPLC
ꢂ
analysis: Chiralcel OD chiral column, mobile phase iso-PrOH/
hexane: 5/95, flow rate: 1.0 mL/min, wavelength: 210 nm; tR
(retention time): 20.772 min for the (R)-isomer, 23.017 min for
the (S)-isomer. IR (neat, cmꢁ1): 3407, 3030, 2923, 2853, 1630,
1469, 1307, 1284, 1123, 1053, 807, 723 cmꢁ1 1H NMR (CDCl3): d
.
4.3.16. (R)-2-Nonadecanol 4t
0.82 (t, 3H, J = 6.8 Hz), 1.12–1.34 (m, 22H), 1.49 (br s, 1H), 1.56–
1.76 (m, 2H), 4.45 (t, 1H, J = 6.8 Hz), 4.70 (br s, 1H), 6.74 (dd, 2H,
J1 = 1.9, J2 = 6.3 Hz), 7.18 (dd, 2H, J1 = 1.9, J2 = 6.3 Hz). 13C NMR
(CDCl3): d 15.00, 23.10, 26.00, 29.40–30.01, 31.20, 38.30, 73.50,
114.20, 126.20, 136.10, 154.19. MS m/z: 41, 65, 77, 95, 107, 123,
133, 305, 306 (M+). Anal. Calcd for C20H34O2: C, 78.38; H, 11.18.
Found: C, 78.22; H, 11.57.
Mp 53.2–53.9 °C, ½a D25
¼ ꢁ10 (c 0.97, CHCl3) ee = 80%. HPLC
ꢂ
analysis: The enantiomeric excess was determined by HPLC analy-
sis using a chiral column after derivatization to the corresponding
benzoate. Chiralcel OD-H chiral column, mobile phase iso-PrOH/
hexane: 0.2/99.8, flow rate: 0.5 mL/min, wavelength: 230 nm; tR
(retention time): 10.158 min for the (S)-isomer, 10.783 min for
the (R)-isomer. IR (neat, cmꢁ1): 3325, 2947, 1483, 1375, 1158,
806, 752 cmꢁ1 1H NMR (CDCl3): d 0.82 (t, 3H, J = 6.8 Hz), 1.12 (d,
.
4.3.12. (R)-1-(2-Furyl)-1-hexadecanol 4n
3H, J = 5.8 Hz), 1.2 (m, 30H), 1.36 (m, 2H), 1.52 (s, 1H), 3.68 (m,
1H). 13C NMR (CDCl3): d 14.32, 22.91, 23.70, 25.99, 29.57, 29.82–
29.91, 32.14, 39.62, 68.43. MS m/z: 43, 45, 57, 71, 97, 111, 125,
207. Anal. Calcd for C19H40O: C, 80.21; H, 14.17. Found: C, 79.63;
H, 15.40.
Mp 58.5–59.4 °C, ½a D25
¼ þ8:3 (c 1.1, CHCl3), ee = 72%. HPLC
ꢂ
analysis: Chiralcel OD chiral column, mobile phase iso-PrOH/hex-
ane: 1.5/98.5, flow rate: 1.0 mL/min, wavelength: 210 nm; tR
(retention time): 10.441 min for the (R)-isomer, 11.301 min for
the (S)-isomer. IR (neat, cmꢁ1): 3346, 3023, 2923, 2853, 1607,
1476, 1276, 1153, 1107, 1046, 846, 753 cmꢁ1 1H NMR (CDCl3): d
.
4.3.17. (R)-3-Octadecanol 4x
Mp 45–47 °C, ½a 2D5
¼ ꢁ18 (c 0.95, CHCl3), ee = 91%. HPLC analy-
ꢂ
0.82 (t, 3H, J = 6.8 Hz), 1.14–1.42 (m, 27H), 1.74–1.82 (m, 2H),
4.70 (t, 1H, J = 6.8 Hz), 6.15 (dd, 1H, J1 = 0.9, J2 = 3.4 Hz), 6.26 (dd,
1H, J1 = 1.9, J2 = 3.4 Hz), 7.30 (dd, 1H, J1 = 0.9, J2 = 1.9 Hz). 13C
NMR (CDCl3): d 14.25, 23.10, 25.90, 29.80–30.01, 32.10, 36.10,
68.00, 106.20, 111.01, 142.10, 157.20. MS m/z: 41, 69, 81, 97,
107, 121, 135, 290, 308 (M+), 309. Anal. Calcd for C20H36O2: C,
77.86; H, 11.76. Found: C, 77.01; H, 11.86.
sis: The enantiomeric excess was determined by HPLC analysis
using a chiral column after derivatization to the corresponding
benzoate. Chiralcel OD-H chiral column, mobile phase iso-PrOH/
hexane: 0.2/99.8, flow rate: 0.5 mL/min, wavelength: 230 nm; tR
(retention time): 10.523 min for the (S)-isomer, 11.030 min for
the (R)-isomer. IR (neat, cmꢁ1): 3325, 2919, 1483, 1375, 1077,
806, 725 cmꢁ1 1H NMR (CDCl3): d 0.82 (t, 3H, J = 7.5 Hz), 0.86 (t,
.
4.3.13. (R)-1-(2-Thenyl)-1-hexadecanol 4p
3H, J = 7.1 Hz), 1.2 (m, 26H), 1.3 (m, 2H), 1.4 (m, 2H), 1.47 (s,
1H), 3.43 (m, 1H). 13C NMR (CDCl3): d 10.03, 14.31, 22.97, 25.88,
29.57, 29.84–30.37, 32.14, 37.21, 73.58. MS m/z: 43, 57, 69, 83,
97, 111, 125, 239, 252. Anal. Calcd for C18H38O: C, 79.93; H,
14.16. Found: C, 79.21; H, 14.12.
Mp 44.9–45.4 °C, ½a D25
¼ þ11:7 (c 1.1, CHCl3), ee = 70%. HPLC
ꢂ
analysis: Chiralcel OD chiral column, mobile phase iso-PrOH/hex-
ane: 1.5/98.5, flow rate: 1.0 mL/min, wavelength: 210 nm; tR
(retention time): 13.557 min for the (R)-isomer, 15.578 min for
the (S)-isomer. IR (neat, cmꢁ1): 3423, 3092, 2923, 2853, 1630,
1479, 1392, 1276, 1084, 1046, 800, 707 cmꢁ1 1H NMR (CDCl3):
.
4.3.18. (R)-4-Heptadecanol 4y
Mp 44–45 °C, ½a 2D5
¼ ꢁ8 (c 0.85, CHCl3), ee = 57%. HPLC analysis:
ꢂ
d 0.82 (t, 3H, J = 6.3 Hz), 1.12–1.42 (m, 26H), 1.48 (br s, 1H),
1.70–1.85 (m, 2H), 4.70 (t, 1H, J = 7.3 Hz), 6.88–6.92 (m, 2H),
7.16 (m, 1H). 13C NMR (CDCl3): d 14.20, 23.10, 25.90, 29.40–
30.01, 32.20, 36.60, 74.20, 124.20, 125.50, 126.40, 147.20. MS
m/z: 55, 79, 97, 113, 123, 139, 151, 281, 306, 324 (M+). Anal. Calcd
for C20H36OS: C, 74.01; H, 11.18; S, 9.88. Found: C, 75.32; H,
10.82; S, 7.83.
The enantiomeric excess was determined by HPLC analysis using a
chiral column after derivatization to the corresponding benzoate.
Chiralcel OD-H chiral column, mobile phase iso-PrOH/hexane:
0.2/99.8, flow rate: 0.5 mL/min, wavelength: 230 nm; tR (retention
time): 10.154 min for the (S)-isomer, 10.845 min for the (R)-iso-
mer. IR (neat, cmꢁ1): 3353, 2920, 1483, 1375, 1158, 1077, 860,