A. Speicher, M. Groh, M. Hennrich, A.-M. Huynh
FULL PAPER
8.7 Hz, 1 H), 7.06 (d, J = 3.0 Hz, 1 H), 6.71 (dd, J = 8.7, 3.0 Hz,
1 H), 4.69 (s, 2 H, CH2OH), 3.80 (s, 3 H, OCH3), 2.20 (br. s, 1
H, CH2OH) ppm. 13C NMR (CDCl3): δ = 159.24, 140.76, 133.11,
114.74, 114.18, 112.47, 64.92 (CH2OH), 55.50 (OCH3) ppm.
HRMS: calcd. for C8H9BrO2 215.9786; found 215.9814.
3.57 g, 95%). HRMS: calcd. for C39H42O8 638.2880; found
638.2878.
Bibenzyl 83: The bibenzyl 83, as a benzyl alcohol, was prepared
from 82 (3.80 g, 5.95 mmol) in a procedure analogous to that used
for the synthesis of 28 and was obtained as a colourless resin
(2.63 g, 88%). 1H NMR (CDCl3): δ = 9.81 (s, 1 H, CHO), 7.63
(dd, J = 8.3, 2.0 Hz, 1 H), 7.41 (d, J = 2.0 Hz, 1 H), 7.18 (d, J =
8.8 Hz, 2 H), 7.12 (d, J = 8.5 Hz, 1 H), 7.11 (d, J = 2.8 Hz, 1 H),
7.10 (d, J = 8.3 Hz, 1 H), 7.06 (d, J = 7.8 Hz, 1 H), 6.94 (d, J =
8.8 Hz, 2 H), 6.89 (dd, J = 8.5, 2.8 Hz, 1 H), 6.86 (dd, J = 7.8,
1.5 Hz, 1 H), 6.75 (d, J = 1.5 Hz, 1 H), 4.40 (br. s, 2 H, CH2OH),
3.97 (s, 3 H, OCH3), 3.86 (s, 3 H, OCH3), 3.72 (s, 3 H, OCH3),
2.97 (s, 4 H, CH2CH2) ppm. 13C NMR (CDCl3): δ = 190.42
(CHO), 159.26, 156.46, 156.10, 154.77, 147.02, 142.70, 140.78,
137.05, 131.48, 131.43, 130.21, 129.86, 129.68, 127.90, 127.21,
121.05, 118.56, 118.49, 113.44, 113.35, 111.96, 111.49, 63.87
(CH2OH), 56.30 (OCH3), 55.76 (OCH3), 55.31 (OCH3), 38.02
(CH2CH2), 37.08 (CH2CH2) ppm. HRMS: calcd. for C31H30O6
498.2042; found 498.2057.
2-(2-Bromo-5-methoxybenzyloxy)tetrahydro-2H-pyran (79): The
THP ether 79 was prepared from the benzyl alcohol 78 (4.50 g,
20.7 mmol) in a procedure analogous to that used for the synthesis
1
of 23 and was obtained as a colourless oil (5.80 g, 93%). H NMR
(CDCl3): δ = 7.41 (d, J = 8.8 Hz, 1 H), 7.10 (d, J = 3.2 Hz, 1 H),
6.70 (dd, J = 8.8, 3.2 Hz, 1 H), 4.78 (d, J = 13.6 Hz, 1 H, Ar–
OCH2), 4.77 (t, J = 3.5 Hz, 1 H, OCHO), 4.54 (d, J = 13.6 Hz, 1
H, Ar–OCH2), 3.93 (m, 1 H, OCH2), 3.80 (s, 3 H, OCH3), 3.58 (m,
1 H, OCH2), 1.93–1.53 (m, 6 H) ppm. 13C NMR (CDCl3): δ =
159.07, 138.92, 133.00, 114.66, 114.24, 112.81, 98.44 (OCHO),
68.47 (Ar–OCH2), 62.22 (OCH2), 55.47 (OCH3), 30.55, 25.46,
19.37 ppm. HRMS: calcd. for C13H17BrO3 300.0361; found
300.0351.
2-{4-Methoxy-2-[(tetrahydro-2H-pyran-2-yloxy)methyl]phenyl}-
4,4,5,5-tetramethyl-1,3,2-dioxaborolane (80): A solution of nBuLi
(2.5 m in n-hexane, 8.10 mL, 20.3 mmol) was added slowly at
–78 °C to a solution of the bromoarene 79 (4.70 g, 15.6 mmol) in
anhydrous THF (80 mL) and the mixture was stirred for an ad-
ditional 60 min. Trimethyl borate (3.25 g, 31.3 mmol) was added in
one portion at –78 °C and the mixture was allowed to warm to r.t.
over 2 h. A solution of saturated aqueous KH2PO4 (100 mL) was
added dropwise and the mixture was extracted with CH2Cl2
(1ϫ80 mL, 2ϫ40 mL). Pinacol (3.79 g, 31.2 mmol) and MgSO4
(37.6 g, 0.31 mol) were added to the combined organic layers and
the mixture was stirred for 12 h. The solid was filtered off and
washed with CH2Cl2 (50 mL), and the filtrate was concentrated
under reduced pressure. The crude material was purified by flash
chromatography (SiO2, n-hexane/EtOAc 4:1 Ǟ 3:1). The boronic
Dehydroisoriccardin D Trimethyl Ether (84): The stilbene 84 was
prepared from 83 (2.00 g, 4.01 mmol) in a procedure analogous to
that used for the synthesis of 40 and was obtained as a colourless
solid (NMR: E isomer only, 750 mg, 40%); m.p. 186 °C. 1H NMR
(CDCl3): δ = 7.22 (d, J = 2.6 Hz, 1 H), 7.21 (dd, J = 8.0, 2.4 Hz,
1 H), 7.16 (d, J = 8.4 Hz, 1 H), 7.01 (dd, J = 8.0, 2.4 Hz, 1 H),
6.99 (dd, J = 8.0, 2.4 Hz, 1 H), 6.91 (d, J = 7.8 Hz, 1 H), 6.90 (dd,
J = 8.0, 2.4 Hz, 1 H), 6.86–6.90 (m, 4 H), 6.70 (dd, J = 7.8, 1.4 Hz,
1 H), 6.52 (d, J = 1.4 Hz, 1 H), 6.32 (d, J = 1.8 Hz, 1 H), 6.21 (d,
J = 16.3 Hz, 1 H), 3.95 (s, 3 H, OCH3), 3.86 (s, 3 H, OCH3), 3.55
(s, 3 H, OCH3), 3.23–3.03 (m, 4 H, CH2CH2) ppm. 13C NMR
(CDCl3): δ = 158.83, 156.44, 152.79, 150.07, 148.44, 141.08, 137.04,
136.42, 131.33, 131.18, 130.79, 130.74, 130.68, 130.29, 126.49,
126.43, 125.68, 122.19, 122.04, 121.78, 120.90, 113.08, 112.19,
111.52, 109.54, 108.50, 56.05 (OCH3), 55.44 (OCH3), 55.25
(OCH3), 35.88 (CH2CH2), 35.43 (CH2CH2) ppm. HRMS: calcd.
for C31H28O4 464.1988; found 464.1992.
1
ester 80 (4.08 g, 75%) was obtained as a colourless oil. H NMR
(CDCl3): δ = 7.76 (d, J = 8.3 Hz, 1 H), 7.09 (d, J = 2.5 Hz, 1 H),
6.79 (dd, J = 8.3, 2.5 Hz, 1 H), 4.94 (d, J = 12.8 Hz, 1 H, Ar–
OCH3), 4.85 (d, J = 12.8 Hz, 1 H, Ar–OCH2), 4.77 (m, 1 H,
OCHO), 3.95 (m, 1 H, OCH2), 3.83 (s, 3 H, OCH3), 3.54 (m, 1 H,
OCH2), 1.91–1.51 (m, 6 H), 1.32 (s, 12 H, CH3) ppm. 13C NMR
Isoriccardin D Trimethyl Ether (85): The stilbene 84 (470 mg,
1.01 mmol) was hydrogenated in a procedure analogous to that
used for the synthesis of 31 and was obtained as a colourless solid
(CDCl3):
δ = 161.99, 147.30, 137.85, 113.43, 111.68, 98.32
1
(OCHO), 83.31 [OC(CH3)2], 68.48 (Ar–OCH2), 62.08 (OCH2),
55.09 (OCH3), 30.73, 25.59, 24.90 (CH3), 24.85 (CH3), 19.51 ppm.
HRMS: calcd. for C19H29BO5 348.2108; found 348.2148.
(448 mg, 95%); m.p. 149 °C. H NMR (CDCl3): δ = 7.16 (dd, J =
8.2, 2.3 Hz, 1 H), 7.03 (d, J = 8.5 Hz, 1 H), 6.97 (dd, J = 8.2,
2.3 Hz, 1 H), 6.92 (d, J = 7.6 Hz, 1 H), 6.89 (dd, J = 8.2, 2.3 Hz,
1 H), 6.87 (d, J = 2.6 Hz, 1 H), 6.81 (d, J = 8.3 Hz, 1 H), 6.80 (dd,
J = 8.2, 2.3 Hz, 1 H), 6.77 (dd, J = 8.3, 2.0 Hz, 1 H), 6.76 (dd, J
= 8.5, 2.6 Hz, 1 H), 6.66 (dd, J = 7.6, 1.4 Hz, 1 H), 6.41 (d, J =
1.4 Hz, 1 H), 5.85 (d, J = 2.0 Hz, 1 H), 3.91 (s, 3 H, OCH3), 3.83
(s, 3 H, OCH3), 3.56 (s, 3 H, OCH3), 3.16 (m, 2 H, CH2CH2), 3.02
(m, 2 H, CH2CH2), 2.71 (m, 1 H, CH2CH2), 2.57 (m, 1 H,
CH2CH2), 2.32 (m, 2 H, CH2CH2) ppm. 13C NMR (CDCl3): δ =
158.86, 156.27, 153.77, 149.75, 147.23, 141.77, 140.86, 136.78,
134.91, 131.31, 130.83, 130.67, 130.47, 130.16, 127.43, 121.61,
121.41, 121.22, 120.84, 115.37, 114.20, 111.83, 111.62, 111.06,
56.14 (OCH3), 55.22 (OCH3), 55.17 (OCH3), 37.29 (CH2CH2),
36.66 (CH2CH2), 36.43 (CH2CH2), 35.46 (CH2CH2) ppm. HRMS:
calcd. for C31H30O4 466.2144; found 466.2159.
2,4Ј-Dimethoxy-2Ј-[(tetrahydro-2H-pyran-2-yloxy)methyl]biphenyl-
4-carbaldehyde (81): The biaryl 81 was prepared from 59 (3.10 g,
10.9 mmol) and 80 (2.93 g, 8.41 mmol) in a procedure analogous
to that used for the synthesis of 26 and was obtained as a yellow
oil (2.23 g, 74%). 1H NMR (CDCl3): δ = 10.01 (s, 1 H, CHO), 7.49
(dd, J = 7.5, 1.5 Hz, 1 H), 7.45 (d, J = 1.5 Hz, 1 H), 7.35 (d, J =
7.5 Hz, 1 H), 7.15 (d, J = 2.8 Hz, 1 H), 7.12 (d, J = 8.4 Hz, 1 H),
6.89 (dd, J = 8.4, 2.8 Hz, 1 H), 4.73–4.49 (br. m, 1 H, Ar–OCH2),
4.65–4.39 (br. m, 1 H, OCHO), 4.35–4.14 (br. m, 1 H, Ar–OCH2),
3.86 (s, 3 H, OCH3), 3.83 (s, 3 H, OCH3), 3.80–3.59 (br. m, 1 H,
OCH2), 3.45–3.31 (br. m,1 H, OCH2), 1.83–1.41 (m, 6 H) ppm. 13
C
NMR (CDCl3): δ = 191.90 (CHO), 159.48, 157.52, 138.32, 136.98,
136.59, 132.02, 130.94, 128.79, 124.10, 113.54, 112.68, 108.99,
98.15 (OCHO), 66.99 (Ar–OCH2), 61.88 (OCH2), 55.71 (OCH3),
55.29 (OCH3), 30.51, 25.42, 19.22 ppm. HRMS: calcd. for
C21H24O5 356.1624; found 356.1578.
Isoriccardin D (14): Isoriccardin D (14) was prepared from its tri-
methyl ether 85 (480 mg, 1.03 mmol) in a procedure analogous to
that used for the synthesis of 8 and was obtained as a colourless
solid (332 mg, 76%); m.p. 285 °C. NMR spectroscopic data; see
Tables 3 and 4. HRMS: calcd. for C28H24O4 424.1675; found
424.1684.
Stilbene 82: The stilbene 82 was prepared from 81 (2.10 g,
2.67 mmol) and 20 in a procedure analogous to that used for the
synthesis of 27 and was obtained as a colourless resin (E/Z mixture,
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Eur. J. Org. Chem. 2010, 6760–6778