H. Zong et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
5
4.2.5. 1-(4-Chlorophenyl)pentan-1-ol19
mined by Chiral GC Chirasil Dex CB [Column temperature:
120 °C, tR = 7.6 min (R), tR = 8.9 min (S)]. 1H NMR (400 MHz, CDCl3):
d 1.50 (d, J = 6.5 Hz, 3H), 3.13 (s, 3H), 4.85 (q, J = 6.5 Hz, 1H), 7.24–
7.48 (m, 5H); 13C NMR (100 MHz, CDCl3): d 25.2, 70.2, 125.5, 127.4,
128.5, 146.0.
Colorless oil, 92% yield, 94% ee was obtained using D-TADDOL as
chiral ligand, [a] [a]
28.5 = +17.4 (c 1.0, C6H6) (Lit.19 22 = +18.3 (c 0.6,
D
D
C6H6) for 87% ee (R)); 87% yield, 92% ee was obtained using (S)-
BINOL as chiral ligand; the ee value was determined by Chiral HPLC
analysis with
a Chiralcel OD-H column [(Hexane/2-propa-
nol = 99/1, 1.0 mL/min, 220 nm); retention time: tR = 16.9 min (S),
tR = 18.3 min (R)]. 1H NMR (400 MHz, CDCl3): d 0.89 (t, J = 7.2 Hz,
3H), 1.14–1.39 (m, 4H), 1.54–1.82 (m, 2H), 2.74 (br, 1H), 4.57 (t,
J = 6.7 Hz, 1H), 7.20–7.25 (m, 2H), 7.27–7.33 (m, 2H); 13C NMR
(100 MHz, CDCl3): d 14.0, 22.6, 27.8, 38.8, 73.9, 127.3, 128.5,
133.0, 143.4.
4.2.11. 1-(4-Fluorophenyl)ethanol22
Colorless oil, 87% yield, 84% ee was obtained using
D-TADDOL as
chiral ligand, [
a]
30.4 = +18.3 (c 1.0, CHCl3) (Lit.22
[
a
]
20 = ꢀ81.5 (c
D
D
1.58, CHCl3) for 96% ee (S)); 76% yield, 8% ee was obtained using
(S)-BINOL as chiral ligand; the ee value was determined by Chiral
GC Chirasil Dex CB [Column temperature: 120 °C, tR = 7.6 min (R),
tR = 8.9 min (S)]. 1H NMR (400 MHz, CDCl3): d 1.47 (d, J = 6.5 Hz,
3H), 2.17 (br, 1H), 4.87 (t, J = 6.4 Hz, 1H), 6.98–7.09 (m, 2H),
7.30–7.39 (m, 2H); 13C NMR (100 MHz, CDCl3): d 25.2, 69.7,
115.2 (d, J = 21.3 Hz), 127.1 (d, J = 8.0 Hz), 114.5 (d, J = 3.0 Hz),
162.1 (d, J = 245.0 Hz); 19F NMR (376 MHz, CDCl3): d ꢀ115.4 (m).
4.2.6. 1-(Naphthalen-2-yl)pentan-1-ol19
White solid, mp 50–51 °C; 83% yield, 86% ee was obtained using
D
-TADDOL as chiral ligand, [
[a]
19 = +33.8 (c 1.52, CHCl3) for 93% ee (R)); 78% yield, 84% ee was
D
a]
29.7 = +13.4 (c 1.0, CHCl3) (Lit.19
D
obtained using (S)-BINOL as chiral ligand; the ee value was deter-
mined by Chiral HPLC analysis with a Chiralcel OD-H column
[(Hexane/2-propanol = 99/1, 1.0 mL/min, 220 nm); retention time:
tR = 47.9 min (S), tR = 54.3 min (R)]. 1H NMR (400 MHz, CDCl3): d
0.94 (t, J = 7.0 Hz, 3H), 1.29–1.47 (m, 4H), 1.73–2.00 (m, 2H), 2.51
(br, 1H), 4.80 (t, J = 7.0 Hz, 1H), 7.45–7.58 (m, 3H), 7.74–7.92 (m,
4H); 13C NMR (100 MHz, CDCl3): d 14.1, 22.7, 28.0, 38.7, 74.8,
127.7, 128.0, 128.3, 133.0, 133.3, 142.4.
4.2.12. 1-p-Tolylethanol20
Colorless oil, 73% yield, 81% ee was obtained using
D-TADDOL as
chiral ligand, [
a
]
D
26.2 = +35.0 (c 1.0, CHCl3); 68% yield, 8% ee was
obtained using (S)-BINOL as chiral ligand; the ee value was deter-
mined by Chiral GC Chirasil Dex CB [Column temperature:
120 °C, tR = 9.3 min (R), tR = 10.4 min (S)]. 1H NMR (400 MHz,
CDCl3): d 1.50 (d, J = 6.5 Hz, 3H), 2.41 (s, 3H), 2.78 (br, 1H), 4.85
(q, J = 6.5 Hz, 1H), 7.16–7.33 (m, 4H); 13C NMR (100 MHz, CDCl3):
d 21.2, 25.1, 70.1, 125.5, 129.1, 137.0, 143.0.
4.2.7. 1-(Thiophen-2-yl)pentan-1-ol20
Colorless oil, 75% yield, 63% ee was obtained using
D-TADDOL as
chiral ligand, [
a
]
D
30.5 = +12.2 (c 1.0, CHCl3); 70% yield, 47% ee was
4.2.13. 1-Phenylheptan-1-ol23
obtained using (S)-BINOL as chiral ligand; the ee value was deter-
mined by Chiral GC Chirasil Dex CB [Column temperature:
130 °C, tR = 16.6 min (S), tR = 17.1 min (R)]. 1H NMR (400 MHz,
CDCl3): d 0.93 (t, J = 7.2 Hz, 3H), 1.20–1.52 (m, 4H), 1.77–1.97 (m,
2H), 2.62 (br, 1H), 4.89 (t, J = 6.6 Hz, 1H), 6.92–7.02 (m, 2H),
7.21–7.27 (m, 1H); 13C NMR (100 MHz, CDCl3): d 14.1, 22.5, 27.9,
39.0, 70.3, 123.7, 124.4, 126.6, 149.1.
Colorless oil, 86% yield, 87% ee was obtained using
D-TADDOL as
chiral ligand, [
a]
30.2 = +25.0 (c 1.0, CHCl3) (Lit.23 26 = +30.0 (c 0.7,
[a]
D
D
CHCl3) for 79% ee (R)); 81% yield, 89% ee was obtained using (S)-
BINOL as chiral ligand; the ee value was determined by Chiral GC
Chirasil Dex CB [Column temperature: 160 °C, tR = 8.8 min (S),
tR = 9.0 min (R)]. 1H NMR (400 MHz, CDCl3): d 0.95 (t, J = 7.1 Hz,
3H), 1.27–1.47 (m, 8H), 1.64–1.96 (m, 2H), 2.76 (s, 1H), 4.55–
4.68 (m, 1H), 7.24–7.45 (m, 5H); 13C NMR (100 MHz, CDCl3): d
14.1, 22.7, 25.8, 29.3, 31.9, 39.2, 74.6, 126.0, 127.4, 128.4, 145.1.
4.2.8. (E)-1-Phenylhept-1-en-3-ol21
Colorless oil, 82% yield, 67% ee was obtained using
D
-TADDOL as
22 = +1.3 (c 0.72,
D
chiral ligand, [
a]
29.8 = ꢀ1.0 (c 1.0, CHCl3) (Lit.21
[a]
4.2.14. (4-(Trifluoromethyl)phenyl)phenylmethanol24
D
CHCl3) for 96% ee (S)); 81% yield, 57% ee was obtained using (S)-
BINOL as chiral ligand; the ee value was determined by Chiral HPLC
Colorless oil, 56% yield, 71% ee was obtained using
D
-TADDOL as
[a]
24 = +35.6 (c 0.3,
D
chiral ligand, [
a
]
D
30.5 = ꢀ25.0 (c 1.0, CHCl3) (Lit.24
analysis with
a
Chiralcel OD-H column [(Hexane/2-propa-
CHCl3) for 92% ee (S)); 61% yield, 73% ee was obtained using (S)-
nol = 90/10, 1.0 mL/min, 220 nm); retention time: tR = 6.9 min (R),
tR = 9.9 min (S)]. 1H NMR (400 MHz, CDCl3): d 0.95 (t, J = 7.2 Hz,
3H), 1.35–1.47 (m, 4H), 1.55–1.76 (m, 2H), 2.01 (br, 1H), 4.26–
4.34 (m, 1H), 6.21–6.29 (m, 1H), 6.60 (d, J = 15.9 Hz, 1H), 7.19–
7.48 (m, 5H); 13C NMR (100 MHz, CDCl3): d 14.1, 22.7, 27.7, 37.1,
73.1, 126.5, 127.6, 128.6, 130.1, 132.7, 136.8.
BINOL as chiral ligand; the ee value was determined by Chiral HPLC
analysis with
a
Chiralcel OJ-H column [(hexane/2-propa-
nol = 90/10, 0.8 mL/min, 220 nm); retention time: tR = 8.3 min (R),
tR = 8.7 min (S)]. 1H NMR (400 MHz, CDCl3): d 3.22 (s, 1H), 5.79
(m, 1H), 7.31–7.43 (m, 5H), 7.45–7.56 (m, 2H), 7.57–7.73 (m,
2H); 13C NMR (100 MHz, CDCl3): d 75.7, 124.2 (q, J = 272.1 Hz),
125.4 (q, J = 3.8 Hz), 126.69, 126.71, 128.1, 128.8, 129.6 (q,
J = 32.4 Hz), 143.1, 147.5. 19F NMR (376 MHz, CDCl3): d ꢀ62.4 (s).
4.2.9. 1-Cyclohexylpentan-1-ol8e
Colorless oil, 12% yield, 68% ee was obtained using D-TADDOL as
chiral ligand, [
a]
24.1 = +6.3 (c 2.0, CHCl3) (Lit.8e
[a]
20 = ꢀ15.4 (c 1.9,
Acknowledgments
D
D
CHCl3) for 90% ee (S)); 15% yield, 52% ee was obtained using (S)-
BINOL as chiral ligand; the ee value was determined by Chiral GC
Chirasil Dex CB [Column temperature: 115 °C, tR = 25.2 min (S),
tR = 26.3 min (R)]. 1H NMR (400 MHz, CDCl3): d 0.88 (t, J = 7.3 Hz,
3H), 0.95–1.47 (m, 12H), 1.57–1.67 (m, 2H), 1.68–1.82 (m, 3H),
1.89 (br, 1H), 3.27–3.34 (m, 1H); 13C NMR (100 MHz, CDCl3): d
14.0, 22.8, 26.2, 26.4, 26.6, 27.7, 28.1, 29.3, 33.8, 43.6, 76.1.
We gratefully acknowledge the financial support from the Nat-
ure Science Foundation of Fujian Province, China (No. 2016J01086),
and The Key Laboratory of Coal to Ethylene Glycol and Its Related
Technology, Fujian Institute of Research on the Structure of Matter,
Chinese Academic of Sciences.
A. Supplementary data
4.2.10. 1-Phenylethanol20
Colorless oil, 80% yield, 82% ee was obtained using
chiral ligand, [
25.6 = +42.1 (c 1.0, CHCl3); 72% yield, 10% ee was
obtained using (S)-BINOL as chiral ligand; the ee value was deter-
D-TADDOL as
Supplementary data associated with this article can be found, in
a]
D