288 J. Chin. Chem. Soc., Vol. 58, No. 3, 2011
Chang
6-(4-(tert-Butyl)diphenylsiloxy)phenyl)hex-1-ene (6)
A solution of compound 5 (4.72 g, 10.4 mmol) in to-
luene (50 mL) was added allylmagnesium chloride (2.0 M
solution in THF, 15.6 mL, 31.2 mmol) at 0 ºC. The reaction
solution was stirred at 95 ºC for 36 h, while the reaction was
monitored by thin-layer chromatography (TLC). The reac-
tion mixture was quenched with cold saturated ammonium
chloride solution (20 mL) at 0 ºC and extracted with ethyl
acetate (3 × 30 mL). The combined organic phases were
dried over anhydrous magnesium sulfate, filtered, and con-
centrated in vacuo to award a yellowish liquid (5.12 g). The
crude product was purified by flash column chromatogra-
phy eluting with hexane/EtOAc (100:1) to give 6 (4.02 g,
93%) as a colorless liquid. IR (KBr) 3072, 2931, 2858,
Hz, 2H), 6.74 (d, J = 8.8 Hz, 2H), 5.54 (dt, J = 14.4, 6.0 Hz,
1H), 5.46 (dt, J = 14.4, 6.0 Hz, 1H), 4.76 (br, 1H), 3.79 (s,
3H), 3.26 (d, J = 6.0 Hz, 2H), 2.52 (t, J = 7.6 Hz, 2H),
2.06-2.01 (m, 2H), 1.60-1.54 (m, 2H), 1.43-1.34 (m, 2H);
13C NMR (150 MHz, CDCl3) d 157.64, 153.50, 134.76,
133.21, 131.41, 129.37, 129.35, 129.33, 115.04, 113.75,
55.26, 38.09, 34.77, 32.24, 31.14, 28.92; MS (EI): m/z 296
(M+); HRMS (EI) m/z Calcd for C20H24O2 296.1777, found
296.1785. Anal. Calcd for C20H24O2: C, 81.00; H, 8.00.
Found: C, 80.73; H, 8.12.
6-(4-Hydroxyphenyl)hex-1-ene (7)
A solution of compound 4 (1.62 g, 7.5 mmol) in tolu-
ene (40 mL) was added allylmagnesium chloride (2.0 M so-
lution in THF, 22.0 mL, 44.0 mmol) at 0 ºC. The reaction
solution was stirred at 95ºC for 42 h, while the reaction was
monitored by TLC. The reaction mixture was quenched
with cold saturated ammonium chloride solution (20 mL)
at 0 ºC and extracted with ethyl acetate (3 × 30 mL). The
combined organic phases were dried over anhydrous mag-
nesium sulfate, filtered, and concentrated in vacuo to award
a yellowish liquid (2.32 g). The crude product was purified
by flash column chromatography eluting with hexane/
EtOAc (15:1) to afford 7 (1.26 g, 95%) as a colorless liq-
uid. IR (KBr) 3546, 3073, 2927, 2854, 1641, 1610, 1513,
1362 cm-1; 1H NMR (400 MHz, CDCl3) d 7.04 (d, J = 10.8
Hz, 2H), 6.75 (d, J = 10.8 Hz, 2H), 5.85-5.75 (m, 1H),
5.02-4.92 (m, 2H), 4.69 (br, 1H), 2.54 (t, J = 7.6 Hz, 2H),
2.10-2.04 (m, 2H), 1.63-1.55 (m, 2H), 1.45-1.37 (m, 2H);
13C NMR (100 MHz, CDCl3) d 153.31, 138.86, 134.86,
129.38, 115.13, 114.31, 34.79, 33.55, 31.05, 28.39; MS
(EI): m/z 176 (M+); HRMS (EI) m/z calcd for C12H16O
176.1202, found 176.1193. Anal. Calcd for C12H16O: C,
81.82; H, 9.00. Found: C, 81.63; H, 9.10.
1
1644, 1510, 1256 cm-1; H NMR (400 MHz, CDCl3) d
7.72-7.70 (m, 4H), 7.41-7.34 (m, 6H), 6.88 (d, J = 8.8 Hz,
2H), 6.66 (d, J = 8.8 Hz, 2H), 5.83-5.72 (m, 1H), 4.99-4.90
(m, 2H), 2.47 (t, J = 7.8 Hz, 2H), 2.06-2.01 (m, 2H), 1.56-
1.50 (m, 2H), 1.40-1.34 (m, 2H), 1.09 (s, 9H); 13C NMR
(100 MHz, CDCl3) d 153.49, 138.89, 135.54, 135.06,
133.23, 129.77, 128.97, 127.68, 119.37, 114.29, 34.89,
33.59, 30.95, 28.45, 26.58, 19.46; MS (EI): m/z 414 (M+);
HRMS (EI) m/z calcd for C28H34SiO 414.2379, found
414.2386; Anal. Calcd for C28H34SiO: C, 81.00; H, 8.00.
Found: C, 81.03; H, 8.03.
Diarylheptanoid 2
A solution of olefin 6 (0.42 g, 1.0 mmol) and 4-al-
lylanisole (0.31 mL, 2.0 mmol) in dry CH2Cl2 (5 mL) was
added via syringe to a stirred solution of Grubbs’ first-gen-
eration catalyst (0.04 g, 0.05 mmol) in dry CH2Cl2 (5 mL)
at ambient temperature. The reaction mixture was stirred at
reflux for 18 h under a nitrogen atmosphere. The solvent
was removed in vacuo and THF (10 mL) was added fol-
lowed by a tetrabutylammonium fluoride solution (1.0 M
solution in THF, 2.0 mL, 2.0 mmol) at ambient tempera-
ture. After stirring for another 2 h, the reaction mixture was
concentrated in vacuo to obtain a dark liquid (1.12 g). The
crude product was purified by flash column chromatogra-
phy eluting with hexane/EtOAc (10:1) to afford a mixture
of 2 and its (Z)-isomer (0.184 g, 62%). The mixture of
alkenes was separated further by flash column chromatog-
raphy on AgNO3-doped silica gel using hexane/EtOAc
(10:1) as the eluent to give the desired diarylheptanoid 2 as
a colorless liquid (0.15 g, 50%) and the (Z)-isomer (0.029
g, 10%). IR (KBr) 3744, 3028, 2931, 2857, 1648, 1510,
1251, 1111, 921 cm-1; 1H NMR (400 MHz, CDCl3) d 7.08
(d, J = 8.4 Hz, 2H), 7.01 (d, J = 8.4 Hz, 2H), 6.83 (d, J = 8.8
Synthesis of Diarylheptanoid 2 from olefin 7
As the previous procedure, a reaction solution of ole-
fin 7 (0.176 g, 1.0 mmol), 4-allylanisole (0.31 mL, 2.0
mmol), and Grubbs’ first-generation catalyst (0.04 g, 0.05
mmol) in dry CH2Cl2 (10 mL) was stirred at reflux for 18 h
under a nitrogen atmosphere. The solvent was removed in
vacuo to obtain the crude product (0.23 g). The crude prod-
uct was purified by flash column chromatography using
hexane/EtOAc (10:1) as the eluent to afford a mixture of 2
and its (Z)-isomer (0.207 g, 70%). The mixture of alkenes
was separated further by flash column chromatography on
AgNO3-doped silica gel using hexane/EtOAc (10:1) as the
eluent to afford the desired diarylheptanoid 2 as a colorless
liquid (0.172 g, 58%) and the (Z)-isomer (0.027 g, 9%).