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Organic & Biomolecular Chemistry
subsequently for 1 hour. The reaction solution was then parti- → 5% EtOAc in LP) afforded 13 (386 mg, 1.15 mmol, 85%) as a
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tioned between satd. aqu. NH4Cl (30 mL) and DCM (30 mL). colorless oil. H NMR (200 MHz, CDCl3) δ 7.15–7.02 (m, 3H),
The aqu. layer was extracted with DCM (2 × 10 mL) and the 6.88–6.79 (m, 2H), 6.76–6.67 (m, 2H), 5.95 (ddt, J = 16.6, 10.2,
combined organic layers were dried over MgSO4, filtered and 6.3 Hz, 1H), 5.69–5.44 (m, 2H), 5.09–4.91 (m, 2H), 3.79 (s, 6H),
volatiles were removed in vacuo. After purification by flash 3.40–3.28 (m, 4H), 2.68–2.56 (m, 2H), 2.24 (q, J = 7.0 Hz, 2H),
column chromatography on silica gel (5% → 15% DCM in LP) 1.69 (p, J = 7.6 Hz, 2H) ppm; 13C NMR (50 MHz, CDCl3)
8 (654 mg, 2.74 mmol, 78%) was obtained as a colorless δ 158.2, 157.9, 142.0, 137.9, 133.2, 130.6, 130.1, 129.8, 129.3
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liquid. H NMR (200 MHz, CDCl3) δ 7.07 (d, J = 9.2 Hz, 1H), (2C), 129.2, 115.4, 115.0, 114.0 (2C), 111.2, 55.4, 55.3, 36.4,
6.75–6.66 (m, 2H), 5.95 (ddt, J = 16.5, 10.2, 6.2 Hz, 1H), 32.7, 30.9, 27.3 ppm; HRMS (ESI) calcd for C23H29O2+ (M + H)+
5.09–4.90 (m, 2H), 3.79 (s, 3H), 3.56 (t, J = 6.3 Hz, 2H), 3.34 (dt, 337.2162, found 337.2163.
J = 6.2, 1.7 Hz, 2H), 2.67–2.55 (m, 2H), 1.94–1.64 (m, 4H) ppm;
(Z)-5,5′-Diallyl-2,2′-dimethoxy-4-(6-(4-methoxyphenyl)hex-4-
13C NMR (50 MHz, CDCl3) δ 158.2, 141.4, 137.8, 130.8, 129.8, en-1-yl)-1,1′-biphenyl (14). Three identical batches were set
115.5, 115.1, 111.3, 55.3, 45.0, 36.4, 32.6, 32.2, 28.1 ppm; up. KHMDS (122 µL, 0.06 mmol, 1.5 equiv., 0.5 M in toluene)
HRMS (ESI) calcd for C14H20ClO+ (M + H)+ 239.1197, found was added to a suspension of Wittig reagent 10 (30 mg,
239.1193.
0.04 mmol, 1 equiv.) in dry diethyl ether (1 mL) under argon at
(4-(2-Allyl-5-methoxyphenyl)butyl)triphenylphosphonium 0 °C. The reaction was stirred for 5 minutes at 0 °C and
iodide (9). A mixture of 8 (113 mg, 0.47 mmol, 1 equiv.), NaI 20 minutes at room temperature. Afterwards, the reaction was
(71 mg, 0.47 mmol, 1 equiv.) and PPh3 (124 mg, 0.47 mmol, 1 cooled to −55 °C and aldehyde 11 (9 mg, 0.06 mmol, 1.5
equiv.) in EtOAc (2.37 mL) under argon was stirred at reflux equiv.) was added as a solution in dry diethyl ether. The reac-
temperature for 65 hours. Volatiles were removed in vacuo. tion was allowed to warm up and was stirred at room tempera-
CHCl3 was added and after stirring for 5 minutes the mixture ture for 5 hours. The three identical batches were combined
was filtered through a pad of Na2SO4. Volatiles were removed and the mixture was dried over MgSO4, filtered and volatiles
in vacuo and after drying in high vacuum, the crude product were removed in vacuo. Purification by flash column chromato-
was obtained as an oil. Stirring with refluxing diethyl ether graphy on silica gel (1% → 5% EtOAc in LP) afforded 14
prompted the oil to crystallize. After cooling to room tempera- (48 mg, 0.10 mmol, 82%) as a colorless oil. 1H NMR (400 MHz,
ture the solvent was decanted and after drying in high vacuum CDCl3) δ 7.16–7.10 (m, 3H), 7.07 (d, J = 2.3 Hz, 1H), 7.03 (s,
9 (210 mg, 0.35 mmol, 75%) was obtained as beige crystals. 1H), 6.90 (d, J = 8.4 Hz, 1H), 6.84 (d, J = 8.6 Hz, 2H), 6.78 (s,
Mp 121.0–124.0 °C; 1H NMR (400 MHz, CDCl3) δ 7.81–7.75 (m, 1H), 6.05–5.90 (m, 2H), 5.67–5.53 (m, 2H), 5.14–5.00 (m, 4H),
9H), 7.71–7.65 (m, 6H), 6.98 (d, J = 8.3 Hz, 1H), 6.69 (d, J = 3.79 (s, 3H), 3.76 (s, 6H), 3.44–3.33 (m, 6H), 2.71–2.64 (m, 2H),
2.7 Hz, 1H), 6.65 (dd, J = 8.3, 2.7 Hz, 1H), 5.84 (ddt, J = 17.2, 2.29 (q, J = 7.1 Hz, 2H), 1.75 (p, J = 7.6 Hz, 2H) ppm; 13C NMR
10.1, 6.2 Hz, 1H), 4.95–4.82 (m, 2H), 3.78–3.67 (m, 5H), 3.22 (101 MHz, CDCl3) δ 158.0, 155.7, 155.6, 140.9, 138.0, 137.9,
(dt, J = 6.3, 1.7 Hz, 2H), 2.60 (t, J = 7.5 Hz, 2H), 1.96 (quin, J = 133.3, 132.7, 131.9, 131.9, 130.2, 129.5, 129.3 (2C), 129.2,
7.5 Hz, 2H), 1.73–1.62 (m, 2H) ppm; 13C NMR (101 MHz, 128.4, 127.9, 125.6, 115.6, 115.5, 114.0 (2C), 112.3, 111.3, 56.0,
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CDCl3) δ 158.2, 140.6, 137.9, 135.2 (d, JCP = 3.0 Hz, 3C), 133.8 56.0, 55.4, 39.6, 36.6, 32.9, 32.8, 31.1, 27.5 ppm; HRMS (ESI)
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(d, JCP = 10.0 Hz, 6C), 130.7, 130.6 (d, JCP = 12.4 Hz, 6C), calcd for C33H39O3+ (M + H)+ 483.2894, found 483.2870.
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129.6, 118.3 (d, JCP = 85.9 Hz, 3C), 115.4, 114.7, 111.9, 55.7,
(Z)-5-Allyl-5′-(6-(2-allyl-5-methoxyphenyl)hex-2-en-1-yl)-2,2′-
36.4, 32.1, 31.0 (d, 2JCP = 15.4 Hz), 23.2 (d, 1JCP = 49.9 Hz), 22.3 dimethoxy-1,1′-biphenyl (15). KHMDS (0.61 mL, 0.31 mmol,
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(d, JCP = 4.4 Hz) ppm; HRMS (ESI) calcd for C32H34OP+ 1.5 equiv., 0.5 M in toluene) was added to a suspension of
(M − I)+ 465.2342, found 465.2352.
Wittig reagent 9 (121 mg, 0.20 mmol, 1 equiv.) in dry diethyl
(4-(5,5′-Diallyl-2,2′-dimethoxy-[1,1′-biphenyl]-4-yl)butyl)tri- ether (1.02 mL) under argon at 0 °C. The reaction was stirred
phenylphosphonium iodide (10). See ref. 14.
2-(4-Methoxyphenyl)acetaldehyde (11). See ref 14.
for 5 minutes at 0 °C and 20 minutes at room temperature.
Afterwards, the reaction was cooled to −55 °C and aldehyde 12
2-(5′-Allyl-2′,6-dimethoxy-[1,1′-biphenyl]-3-yl)acetaldehyde (91 mg, 0.31 mmol, 1.5 equiv.) was added as a solution in dry
(12). See ref. 14. diethyl ether. The reaction was allowed to warm up and was
(Z)-1-Allyl-4-methoxy-2-(6-(4-methoxyphenyl)hex-4-en-1-yl) stirred at room temperature for 5 hours. The mixture was dried
benzene (13). KHMDS (4.05 mL, 2.03 mmol, 1.5 equiv., 0.5 M over MgSO4, filtered and volatiles were removed in vacuo.
in toluene) was added to a suspension of Wittig reagent 9 Purification by flash column chromatography on silica gel (1%
(800 mg, 1.35 mmol, 1 equiv.) in dry diethyl ether (6.75 mL) → 5% EtOAc in LP) afforded 15 (79 mg, 0.16 mmol, 80%) as a
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under argon at 0 °C. The reaction was stirred for 5 minutes at colorless oil. H NMR (400 MHz, CDCl3) δ 7.14–7.10 (m, 2H),
0 °C and 20 minutes at room temperature. Afterwards, the 7.07–7.03 (m, 3H), 6.89 (dd, J = 8.4, 2.0 Hz, 2H), 6.73 (d, J =
reaction was cooled to −55 °C and aldehyde 11 (304 mg, 2.7 Hz, 1H), 6.70 (dd, J = 8.2, 2.8 Hz, 1H), 6.04–5.87 (m, 2H),
2.03 mmol, 1.5 equiv.) was added as a solution in dry diethyl 5.67–5.49 (m, 2H), 5.12–4.93 (m, 4H), 3.77 (s, 3H), 3.75 (s, 3H),
ether. The reaction was allowed to warm up and was stirred at 3.74 (s, 3H), 3.40–3.29 (m, 6H), 2.63–2.57 (m, 2H), 2.23 (dt, J =
room temperature for 5 hours. The mixture was dried over 7.9, 6.4 Hz, 2H), 1.72–1.63 (m, 2H) ppm; 13C NMR (101 MHz,
MgSO4, filtered and volatiles were removed in vacuo. CDCl3) δ 158.2, 155.6, 155.5, 142.0, 137.9, 137.9, 132.8, 131.9,
Purification by flash column chromatography on silica gel (1% 131.7, 131.5, 130.6, 130.1, 129.8, 129.2, 128.5, 128.3, 128.0,
Org. Biomol. Chem.
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