JOURNAL OF CHEMICAL RESEARCH 2017 299
( )-(E)-3-(7-Methoxy-2-(3-methoxy-4-((tetrahydro-2H-pyran-2-yl)
oxy)phenyl)-3-(((4-(methoxymethoxy)benzoyl)oxy)methyl)-2,3-
dihydrobenzofuran-5-yl)allyl 4-(methoxymethoxy)benzoate (10)
a nitrogen atmosphere. After the solution had been stirred at room
temperature for 2 h a solution of compound 11 (0.11 g, 0.25 mmol)
and DMAP (0.0152 g, 0.125 mmol) in CH2Cl2 (20 mL) was added.
The reaction mixture was stirred and the course of the reaction was
monitored by TLC. On completion of the reaction, water (5 mL) was
added and the aqueous mixture was extracted with AcOEt (3 × 10 mL).
The combined organic extracts were washed with brine (10 mL), dried
over MgSO4 and the solvent was removed under reduced pressure to
leave the crude product. The residue was purified by silica gel column
chromatography (petroleum/acetic ether = 1/2) to give the desired
compound 12: Faint yellow oil; yield 0.119 g (79%); 1H NMR (CDCl3);
δ 1.60–2.17 (m, 6H, CH2CH2CH2 ), 3.51 (s, 3H, OCH3), 3.59–3.64 (m,
2H, OCH2 ), 3.77 (s, 3H, ArOCH3), 3.95 (s, 3H, ArOCH3), 3.75–3.83
(m, 1H, H-3), 4.56 (dd, 1H, J = 11.2 Hz, 7.7 Hz, 3-CH2), 4.66 (dd,
1H, J = 11.2 Hz, 4.9 Hz, 3-CH2), 5.23 (s, 2H, OCH2O), 5.38 (s, 1H,
OCHO), 5.67 (d, 1H, J = 6.8 Hz, H-2), 6.59 (dd, 1H, J = 15.8 Hz,
7.7 Hz, ArCH=CH), 6.91–7.13 (m, 9H, ArH), 7.41 (d, 1H, J = 15.8 Hz,
ArCH=CH), 7.91 (d, 1H, J = 8.0 Hz, CHO); 13C NMR (125 MHz,
CDCl3); δ 18.7, 25.2, 30.2, 50.2, 56.1, 62.1, 65.5, 89.3, 94.1, 97.5, 110.4,
112.4, 115.8, 117.8, 118.4, 118.7, 122.9, 126.6, 128.3, 128.8, 130.8, 131.6,
133.9, 144.8, 146.6, 150.5, 151.3, 152.7, 161.3, 165.8, 193.3; HRMS
calcd for C34H36O10: 604.2303; found: 604.2309.
A mixture of acid 9 (0.114 g, 0.626 mmol) and CDI (0.101 g, 6.23 mmol)
in dry CH2Cl2 (20 mL) in a nitrogen atmosphere at room temperature
was stirred for 2 h and a solution of compound 6 (0.113 g, 0.26 mmol) and
4-dimethylaminopyridine (DMAP) (0.0153 g, 0.125 mmol) in CH2Cl2
(10 mL) was added dropwise. The resulting solution was stirred at room
temperature until TLC showed complete disappearance of compound 6.
Water (5 mL) was then added, and the aqueous mixture was extracted with
AcOEt (3 × 10 mL). The combined organic extracts were washed with
brine (10 mL), dried over MgSO4 and the solvent removed under reduced
pressure to leave the crude product, which was purified by chromatography
on a silica gel column (petroleum/acetic ether = 2/1) to give the desired
compound 10: Yellow oil; yield 0.148 g (75%); 1H NMR (500 MHz,
CDCl3); δ 1.59–1.86 (m, 6H, CH2CH2CH2), 3.48 (s, 6H, 2 × OCH3),
3.71 (s, 3H, ArOCH3), 3.73 (m, 2H, OCH2), 3.85 (s, 3H, ArOCH3), 3.93
(m, 1H, H-3), 4.55 (dd, 1H, J = 11.2 Hz, J = 8.0 Hz, 3-CH2), 4.71 (dd, 1H,
J = 11.2 Hz, J = 4.8 Hz, 3-CH2), 4.94 (m, 2H, ArCH=CHCH2), 5.20 (m,
1H, H-2), 5.22 (s, 4H, 2 × OCH2O), 5.36 (t, 1H, OCHO), 6.28 (m, 1H,
ArCH=CH ), 6.64 (d, 1H, J = 15.8 Hz, ArCH=CH), 6.91–8.03 (m, 13H,
ArH); 13C NMR (125 MHz, CDCl3); δ 18.8, 25.2, 30.2, 50.5, 56.2, 61.6,
64.2, 65.3, 65.8, 88.8, 94.0, 97.3, 110.1, 110.7, 118.0, 118.8, 119.5, 119.8,
121.4, 122.3, 122.5, 123.2, 123.6, 127.6, 128.2, 129.8, 131.6, 132.3, 133.6,
134.1, 145.4, 145.8, 146.3, 149.7, 150.0, 161.0, 165.6 (C=O), 166.0 (C=O);
HRMS calcd for C43H46O13: 770.2933; found: 770.2942.
4,9-Dihydroxy-9-(p-hydroxybenzoyloxy)-3,5’-dimethoxy-4,7’-epoxy-
8,5’-neolignan-7-en-9’-al (2)
In a 25 mL round-bottom flask a mixture of compound 12 (0.060 g,
0.1 mmol), PPTS (2.52 mg, 0.01 mmol) and anhydrous ethanol
(10 mL) was stirred at 60 °C for 1 h and then the solvent was removed
in vacuo to leave the crude product. Then a solution of hydrochloric
acid (4 mL) in THF was added, the mixture was stirred for 1 h at
room temperature and the solvent was concentrated in vacuo. The
crude product was purified by flash chromatography to give the title
Quiquesetinerviusin A (1)
A mixture of compound 10 (0.077 g, 0.1 mmol), PPTS (2.52 mg,
0.011 mmol) and anhydrous ethanol (10 mL) was stirred at 60 °C for 1 h and
the solvent removed in vacuo to leave the crude product. Then a solution
of hydrochloric acid (4 mL) in THF was added, the mixture stirred in a
nitrogen atmosphere for 1 h at room temperature and then concentrated in
vacuo. The crude product was purified by flash chromatography to give
the title compound quiquesetinerviusin A (1): White powder; yield 44.2
mg (74%); 1H NMR (500MHz, CDCl3), δ: 3.70 (s, 3H, Ar-OCH3), 3.88 (m,
1H, H-3), 3.90 (s, 3H, Ar-OCH3), 4.55 (dd, 1H, J = 11.2, J = 8.0Hz, 3-CH2),
4.71 (dd, 1H, J = 11.2, J = 4.8Hz, 3-CH2), 4.90 (m, 2H, ArCH=CHCH2),
5.40 (d, J = 6.8Hz, 1H, 2-H), 6.27 (m, 1H, ArCH=CH), 6.65 (d, 1H, J =
15.5, ArCH=CH), 6.95-7.94 (m, 13H, ArH); 13C NMR (125 MHz, CDCl3):
δ: 50.9, 56.2, 56.4, 65.7, 66.2, 89.7, 110.8, 112.6, 116.2, 116.9, 117.7, 119.6,
120.8, 121.4, 122.5, 122.9, 129.4, 132.3, 132.7, 132.9, 133.8, 135.4, 145.4,
146.9, 148.6, 149.5, 163.5, 163.9, 167.7, 168.2; HRMS calcd for C34H30O10:
598.1834; found: 598.1841. The spectral data are consistent with the
literature.4,19
1
compound 2: White powder; yield 40.5 mg (85%); H NMR (CDCl3);
δ 3.76 (s, 3H, ArOCH3), 3.92 (s, 3H, ArOCH3), 3.74–3.82 (m, 1H, H-3),
4.53 (dd, 1H, J = 11.2 Hz, 7.7 Hz, 3-CH2), 4.63 (dd, 1H, J = 11.2 Hz,
4.9 Hz, 3-CH2), 5.65 (d, 1H, J = 6.8 Hz, H-2), 6.62 (dd, 1H, J = 15.8 Hz,
7.7 Hz, ArCH=CH), 6.89–7.23 (m, 9H, ArH), 7.49 (d, 1H, J = 15.8 Hz,
ArCH=CH), 7.93 (d, 1H, J = 8.0 Hz, CHO); 13C NMR (125 MHz,
CDCl3); δ 50.6, 56.8, 65.7, 90.2, 110.2, 112.1, 115.6, 117.8, 118.5, 118.9,
130.0, 126.4, 128.5, 128.7, 130.6, 131.4, 140.1, 144.5, 146.3, 150.2,
151.6, 152.5, 162.4, 166.3, 193.2; HRMS calcd for C27H24O8: 476.1466;
found: 476.1470. The data are consistent with the literature.4,20
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 21472105).
( )-(E)-3-(3-(Hydroxymethyl)-7-methoxy-2-(3-methoxy-4-((tetrahydro-2H-
pyran-2-yl)oxy)phenyl)-2,3-dihydrobenzofuran-5-yl) acrylaldehyde (11)
Received 12 January 2017; accepted 5 April 2017
Paper 1704528
Published online: 4 May 2017
To a solution of compound 6 (0.22 g, 0.5 mmol) in dry THF (30 mL) were
added fresh MnO2 (0.174 g, 1.0 mmol) and SiO2 (0.174 g, 2.9 mmol) in
a nitrogen atmosphere at room temperature. After stirring for 20 h the
mixture was filtered and evaporated under reduced pressure to give a
yellow oil, which was purified by flash chromatography (petroleum/acetic
ether = 2/3) to give compound 11: Yellow oil; yield 0.199 g (91%); 1H NMR
(500 MHz, CDCl3); δ 1.53–1.89 (m, 6H, CH2CH2CH2), 3.56–3.69 (m, 2H,
OCH2), 3.83–3.91 (m, 1H, H-3), 3.83 (s, 3H, OCH3), 3.93 (s, 3H, OCH3),
3.95–4.05 (m, 2H, OCH2), 5.38 (t, 1H, OCHO), 5.65 (d, J = 6.9 Hz, 2H,
H-2), 6.61 (dd, J = 15.8 Hz, J = 7.7 Hz, 1H, ArCH=CH), 6.90–7.12 (m, 5H,
ArH), 7.42 (d, J = 15.8 Hz, 1H, ArCH=CH), 9.65 (d, J = 7.7 Hz, 1H, CHO);
13C NMR (125 MHz, CDCl3); δ 19.7, 25.2, 30.2, 50.7, 56.0, 56.1, 62.3,
63.9, 88.9, 94.4, 108.7, 112.4, 114.5, 118.1, 119.4, 126.5, 128.0, 129.1, 132.2,
114.8, 146.7, 151.3, 152.8, 153.1, 193.4 (C=O); HRMS calcd for C25H28O7:
440.1830; found: 440.1812.
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