Molecules 2016, 21, 112
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in a well-dried 10mL flask. The mixture was stirred at room temperature for 16 h, and then a Ti(OiPr)4
solution (103.6 L, 0.35 mmol, 1.0 eq.) was slowly added in. After additional 2 h, (Z)-dec-2-enal
µ
(54.0 µL, 0.35 mmol, 1.0 eq.) was added and the mixture was stirred for 4 h at room temperature. The
reaction was quenched with saturated ammonium chloride (5 mL). The resulting mixture was extracted
with methylene chloride (5 mL
product was obtained by purification with column chromatograph (petroleum ether/AcOEt, 10:1,
ˆ
3), dried over sodium sulfate and concentrated under vacuum. Final
20
1
v/v) to give 7a as light yellow oil in 17% yield. rαsD = 84.1 (c = 0.9, in CH2Cl2). dr = 14:1. H-NMR
(400 MHz, CDCl3) 8.07 (m, 2H), 7.58 (m, 1H), 7.45 (m, 2H), 6.18 (d, J = 5.6 Hz, 1H), 6.00 (m, 1H),
δ
5.95–5.84 (m, 1H), 5.64 (d, J = 17.2 Hz, 1H), 5.56 (dd, J = 17.2, 6.0 Hz, 1H), 5.41 (d, J = 10.0 Hz, 1H),
4.89 (t, J = 6.0 Hz, 1H), 2.05 (m, 2H), 1.93 (m, 1H), 1.37 (m, 2H), 1.29 (m, 8H), 0.88 (t, J = 6.8 Hz, 3H).
13C-NMR (100 MHz, CDCl3)
δ 165.1, 135.4, 133.4, 132.0, 129.9, 129.4, 128.5, 127.5, 119.8, 79.5, 74.9,
71.0, 69.6, 65.0, 63.3, 32.0, 31.8, 29.1, 29.1, 28.8, 22.7, 14.1. HRMS [C24H28NaO3]+ calcd for 387.1936,
Found 387.1923.
3.12. Preparation of 3-Hydroxyheptadeca-1-en-4,6-diyn-8-yl benzoate 7b
Under the protection of nitrogen, tetradeca-1,3-diyn-5-yl benzoate 6d (192
µL, 0.6 mmol, 3.0 eq.),
dicyclohexylamine (2.0 L, 0.01 mmol, 0.05 eq.) and diethyl zinc (0.3 mL, 2 M in toluene, 0.6 mmol,
µ
3.0 eq.) were sequentially added to an ether (4 mL) solution of R-BINOL (22.9 mg, 0.08 mmol, 0.4 eq.)
in a well-dried 10 mL flask. The mixture was stirred at room temperature for 16 h, and then a Ti(OiPr)4
solution (59 µL, 0.2 mmol, 1.0 eq.) was slowly added in. After additional 2 h, acraldehyde (13.4 µL,
0.2 mmol, 1.0 eq.) was added and the mixture was stirred for 4 h at room temperature. The reaction
was quenched with saturated ammonium chloride (5 mL). The resulting mixture was extracted with
methylene chloride (5 mL
product was obtained by purification with column chromatograph (petroleum ether/AcOEt, 10:1,
V/V) which gave 7b as light yellow oil in 61% yield. dr > 99:1. H-NMR (400 MHz, CDCl3)
ˆ
3), dried over sodium sulfate and concentrated under vacuum. The final
1
δ 8.05 (m,
2H), 7.63–7.53 (m, 1H), 7.45 (m, 2H), 5.93 (m, 1H), 5.65 (t, J = 6.4 Hz, 1H), 5.47 (d, J = 17.2 Hz, 1H), 5.25
(d, J = 10.0 Hz, 1H), 4.93 (t, J = 5.6 Hz, 1H), 2.16 (d, J = 6.0 Hz, 1H), 1.98–1.85 (m, 2H), 1.57–1.46 (m,
2H), 1.35–1.24 (m, 12H), 0.88 (t, J = 6.8 Hz, 3H). 13C-NMR (100 MHz, CDCl3)
δ 165.4, 135.7, 133.3, 129.8,
129.6, 128.4, 117.4, 78.1, 77.5, 70.2, 69.3, 64.7, 63.5, 34.6, 31.9, 29.5, 29.4, 29.3, 29.1, 25.0, 22.7, 14.1. HRMS
[C24H30NaO3]+ calcd for 389.2093, Found 389.2091.
3.13. Preparation of (E)-3-Hydroxy-1-phenylheptadeca-1-en-4,6-diyn-8-yl benzoate 7c
Under the protection of nitrogen, tetradeca-1,3-diyn-5-yl benzoate 6d (192
µL, 0.6 mmol, 3.0 eq.),
dicyclohexylamine (2.0 L, 0.01 mmol, 0.05 eq.) and diethyl zinc (0.3 mL, 2 M in toluene, 0.6 mmol,
µ
3.0 eq.) were sequentially added to an ether (4 mL) solution of R-BINOL (22.9 mg, 0.08 mmol, 0.4 eq.)
in a well-dried 10 mL flask. The mixture was stirred at room temperature for 16 h, and Ti(OiPr)4
(59 µL, 0.2 mmol, 1.0 eq.) was slowly added in. After additional 2 h, cinnamaldehyde (25.2 µL,
0.2 mmol, 1.0 eq.) was added and the mixture was stirred for 4 h at room temperature. The reaction
was quenched with saturated ammonium chloride (5 mL). The resulting mixture was extracted with
methylene chloride (5 mL
product was obtained by purification with column chromatograph (petroleum ether/AcOEt, 10:1,
ˆ
3), dried over sodium sulfate and concentrated under vacuum. The final
v/v) which gave 7c as light yellow oil in 97% ˝yield. dr = 6:1. HPLC analysis: Chiralcel OD-3 column,
F = 0.8 mL/min, hexane/iPrOH = 94:6, T = 30 C,
λ
= 254 nm, t1 = 51.8 min, t2 = 53.2 min, t3 = 58.3 min
,
1
t4 = 62.2 min. H-NMR (400 MHz, CDCl3)
δ 8.05 (dt, J = 6.8, 0.8 Hz, 2H), 7.63–7.53 (m, 1H), 7.45 (m,
2H), 7.42–7.36 (m, 2H, 7.36–7.30 (m, 2H), 7.30–7.26 (m, 1H), 6.76 (d, J = 16.0 Hz, 1H), 6.25 (dd, J = 16.0,
6.0 Hz, 1H), 5.66 (t, J = 6.4 Hz, 1H), 5.11 (t, J = 6.0Hz, 1H), 2.09–2.01 (m, 1H), 1.93 (m, 2H), 1.52 (m, 2H),
1.40–1.22 (m, 12H), 0.88 (t, J = 6.8 Hz, 3H). 13C-NMR (100 MHz, CDCl3)
δ 165.4, 135.8, 133.3, 132.8,
129.8, 129.6, 128.6, 128.4, 128.3, 126.9, 126.7, 78.1, 77.8, 70.4, 69.3, 64.7, 63.3, 34.6, 31.9, 29.5, 29.4, 29.3,
29.1, 25.0, 22.7, 14.1. HRMS [C30H34NaO3]+ calcd for 465.2406, Found 465.2391.