G. Wei, B. Yu
FULL PAPER
(d, J = 9.0 Hz, 1 H), 7.15 (d, J = 7.5 Hz, 2 H), 5.66 (s, 1 H), 4.30
(br. s, 1 H), 4.08 (dd, J = 8.7, 4.5 Hz, 1 H), 3.98 (br. s, 1 H), 3.66
(dd, J = 11.7, 3.9 Hz, 1 H), 3.62 (dd, J = 11.7, 4.8 Hz, 1 H), 2.28
(s, 3 H) ppm. MS (ESI): m/z = 401.0 [M + H]+, 423.0 [M + Na]+.
HRMS (MALDI): calcd. for C21H21O8+ 401.1231; found 401.1235.
7.48 (br. s, 4 H), 7.31 (d, J = 9.0 Hz, 1 H), 5.75 (s, 1 H), 4.40 (br.
s, 1 H), 4.17 (dd, J = 8.7, 4.5 Hz, 1 H), 4.07 (m, 1 H), 3.79 (dd, J
= 11.7, 3.9 Hz, 1 H), 3.71 (dd, J = 11.7, 5.1 Hz, 1 H), 1.53 (s, 9 H)
ppm. MS (ESI): m/z = 502.0 [M + H]+, 524.0 [M + Na]+. HRMS
(MALDI): calcd. for C25H27O10NNa+ 524.1527; found 524.1532.
7,8-Dihydroxy-2Ј-methylisoflavone
7-O-α-D-Arabinofuranoside
7,8-Dihydroxy-4Ј-trifluoromethylisoflavone 7-O-α-D-Arabinofurano-
(22f): Yield: 18 mg, 34%. Rf = 0.39 (CHCl3/MeOH, 10:1). [α]2D4
=
side (22m): Yield: 24 mg, 41%. Rf = 0.43 (CHCl3/MeOH, 10:1).
52.1 (c = 0.10, MeOH). 1H NMR (300 MHz, CD3OD): δ = 8.13
(s, 1 H), 7.40 (d, J = 8.7 Hz, 1 H), 7.34–7.16 (m, 5 H), 5.71 (s, 1
H), 4.39 (br. s, 1 H), 4.20 (dd, J = 8.7, 4.5 Hz, 1 H), 4.03 (m, 1 H),
3.76 (dd, J = 11.7, 3.9 Hz, 1 H), 3.67 (dd, J = 11.7, 5.1 Hz, 1 H),
2.21 (s, 3 H) ppm. MS (ESI): m/z = 401.2 [M + H]+, 423.2 [M +
Na]+, 439.0 [M + K]+. HRMS (MALDI): calcd. for C21H20O8Na+
423.1050; found 423.1058.
1
[α]2D4 = 37.5 (c = 0.23, MeOH). H NMR (300 MHz, CDCl3): δ =
8.41 (s, 1 H), 7.83–7.65 (m, 4 H), 7.57 (d, J = 8.4 Hz, 1 H), 7.32
(d, J = 7.8 Hz, 1 H), 5.77 (s, 1 H), 4.42 (br. s, 1 H), 4.21 (dd, J =
7.8, 4.5 Hz, 1 H), 4.09 (m, 1 H), 3.82–3.74 (m, 2 H) ppm. 13C NMR
(75 MHz, CD3OD): δ = 178.3, 156.4, 150.3, 149.1, 140.6, 138.1,
131.1, 126.4, 124.6, 121.7, 116.4, 115.1, 109.3, 88.9, 82.8, 79.0, 63.4,
31.0 ppm. MS (ESI): m/z = 455.0 [M + H]+, 477.0 [M + Na]+.
HRMS (ESI): calcd. for C21H17O8F3Na+ 477.0768; found
477.0768.
7,8-Dihydroxy-3Ј-methylisoflavone
7-O-α-D-Arabinofuranoside
(22g): Yield: 30 mg, 58%. Rf = 0.35 (CHCl3/MeOH, 10:1). [α]2D4
=
1
17.7 (c = 0.13, MeOH). H NMR (300 MHz, CD3O D): δ = 8.32
(s, 1 H), 7.78–7.63 (m, 2 H), 7.42–7.29 (m, 3 H), 7.22 (br. s, 1 H),
5.79 (s, 1 H), 4.43 (br. s, 1 H), 4.21 (dd, J = 8.7, 4.5 Hz, 1 H), 4.10
(m, 1 H), 3.78 (dd, J = 11.7, 3.9 Hz, 1 H), 3.71 (dd, J = 11.7,
5.1 Hz, 1 H), 2.41 (s, 3 H) ppm. MS (ESI): m/z = 401.2 [M + H]+,
423.2 [M + Na]+, 439.2 [M + K]+. HRMS (ESI): calcd. for
C21H20O8Na+ 423.1050; found 423.1051.
7,8-Dihydroxy-4Ј-trimethylsilylisoflavone 7-O-α-D-Arabinofurano-
side (22n): Yield: 18 mg, 30%. Rf = 0.58 (CH2Cl2/MeOH, 8:1).
[α]2D4 = 49.1 (c = 0.12, MeOH). 1H NMR (300 MHz, CD3OD): δ =
8.32 (s, 1 H), 7.71–7.46 (m, 5 H), 7.32 (d, J = 8.7 Hz, 1 H), 5.76
(s, 1 H), 4.42 (br. s, 1 H), 4.21 (dd, J = 8.7, 4.5 Hz, 1 H), 4.07 (br.
s, 1 H), 3.86–3.64 (m, 2 H), 0.30 (s, 9 H) ppm. MS (ESI): m/z =
459.0 [M + H]+.
4Ј,7,8-Trihydroxyisoflavone 7-O-α-
D-Arabinofuranoside (22h, A-
5,7-Dihydroxyisoflavone 7-O-α-D-Arabinofuranoside (23a): Yield:
76202):[11,12] Yield: 25 mg, 48%.
14 mg, 28%, procedure A; 8 mg, 16%, procedure B. Rf = 0.42
(CH2Cl2/MeOH, 10:1). [α]2D4 = 86.7 (c = 0.15, MeOH). H NMR
1
3Ј,7,8-Trihydroxyisoflavone 7-O-α-D-Arabinofuranoside (22i): Yield:
18 mg, 35%. Rf = 0.23 (CHCl3/MeOH, 8:1). [α]2D4 = 99.7 (c = 0.08,
(300 MHz, CD3OD): δ = 8.20 (s, 1 H), 7.56 (d, J = 6.6 Hz, 2 H),
7.48–7.34 (m, 3 H), 6.70 (br. s, 1 H), 6.50 (br. s, 1 H), 5.65 (s, 1 H),
4.29 (br. s, 1 H), 4.13–3.96 (m, 2 H), 3.78 (dd, J = 12.0, 2.4 Hz, 1
H), 3.69 (dd, J = 12.0, 4.5 Hz, 1 H) ppm. MS (ESI): m/z = 387.0
1
MeOH). H NMR (300 MHz, CD3OD): δ = 8.31 (s, 1 H), 7.67 (d,
J = 8.7 Hz, 1 H), 7.37 (d, J = 8.7 Hz, 1 H), 7.28 (t, J = 7.5 Hz, 1
H), 7.05 (br. s, 1 H), 7.03 (d, J = 8.1 Hz, 1 H), 6.85 (br. d, J =
6.6 Hz, 1 H), 5.79 (s, 1 H), 4.43 (br. s, 1 H), 4.22 (dd, J = 8.7,
4.5 Hz, 1 H), 4.11 (m, 1 H), 3.79 (dd, J = 11.7, 3.9 Hz, 1 H), 3.74
(dd, J = 11.7, 5.1 Hz, 1 H) ppm. 13C NMR (75 MHz, CD3OD): δ
= 178.6, 158.8, 155.7, 150.0, 148.7, 138.9, 134.9, 130.7, 126.2, 121.7,
117.7, 116.5, 116.4, 116.2, 109.4, 88.9, 83.0, 79.0, 63.4 ppm. MS
(ESI): m/z = 403.0 [M + H]+, 425.0 [M + Na]+. HRMS (MALDI):
+
[M + H]+, 409.0 [M + Na]+. HRMS (ESI): calcd. for C20H19O8
387.1074; found 387.1075.
5,7-Dihydroxy-4Ј-methoxyisoflavone
7-O-α-D-Arabinofuranoside
(23b): Yield: 23 mg, 43%, procedure A. Rf = 0.48 (CH2Cl2/MeOH,
10:1). [α]2D4 = 68.6 (c = 0.19, MeOH). 1H NMR (300 MHz,
CD3OD): δ = 8.17 (s, 1 H), 7.50 (d, J = 7.2 Hz, 2 H), 6.99 (d, J =
7.2 Hz, 2 H), 6.69 (br. s, 1 H), 6.50 (br. s, 1 H), 5.67 (s, 1 H), 4.31
(br. s, 1 H), 4.13–4.02 (m, 2 H), 3.84 (s, 3 H), 3.80 (dd, J = 12.0,
3.0 Hz, 1 H), 3.73 (dd, J = 12.0, 4.5 Hz, 1 H) ppm. MS (ESI): m/z
= 417.0 [M + H]+, 439.0 [M + Na]+. HRMS (MALDI): calcd. for
+
calcd. for C20H19O9 403.1024; found 403.1028.
4Ј-Fluoro-7,8-dihydroxyisoflavone 7-O-α-D-Arabinofuranoside (22j):
Yield: 16 mg, 31%. Rf = 0.42 (CHCl3/MeOH, 8:1). [α]2D4 = 31.6 (c
1
= 0.16, MeOH). H NMR (300 MHz, CD3OD): δ = 8.34 (s, 1 H),
+
C21H21O9 417.1180; found 417.1186.
7.65–7.56 (m, 3 H), 7.34 (d, J = 9.0 Hz, 1 H), 7.19 (t, J = 8.4 Hz,
2 H), 5.77 (s, 1 H), 4.41 (br. s, 1 H), 4.21 (dd, J = 8.7, 4.5 Hz, 1
H), 4.09 (m, 1 H), 3.78 (dd, J = 11.7, 3.9 Hz, 1 H), 3.73 (dd, J =
11.7, 5.1 Hz, 1 H) ppm. MS (ESI): m/z = 405.2 [M + H]+, 427.2 [M
+ Na]+. HRMS (ESI): calcd. for C20H17O8FNa+ 427.0800; found
427.0795.
5,7-Dihydroxy-2Ј-methoxyisoflavone
7-O-α-D-Arabinofuranoside
(23c): Yield: 21 mg, 39%, procedure A. Rf = 0.49 (CH2Cl2/MeOH,
10:1). [α]2D4 = 74.6 (c = 0.19, MeOH). 1H NMR (300 MHz,
CD3OD): δ = 8.28 (s, 1 H), 7.63 (t, J = 8.4 Hz, 1 H), 7.50 (d, J =
7.2 Hz, 1 H), 7.30 (d, J = 8.4 Hz, 1 H), 7.24 (t, J = 7.2 Hz, 1 H),
6.93 (d, J = 1.8 Hz, 1 H), 6.74 (d, J = 1.8 Hz, 1 H), 5.89 (s, 1 H),
4.53 (d, J = 2.1 Hz, 1 H), 4.35–4.22 (m, 2 H), 4.04 (dd, J = 12.0,
3.0 Hz, 1 H), 4.03 (s, 3 H), 3.93 (dd, J = 12.0, 4.5 Hz, 1 H) ppm.
MS (ESI): m/z = 417.2 [M + H]+. HRMS (ESI): calcd. for
4Ј-Dimethylamino-7,8-dihydroxyisoflavone 7-O-α-D-Arabinofurano-
side (22k): Yield: 20 mg, 36%. Rf = 0.30 (CHCl3/MeOH, 10:1).
1
[α]2D4 = 104.6 (c = 0.10, MeOH). H NMR (300 MHz, CD3OD): δ
= 8.22 (s, 1 H), 7.43 (d, J = 8.4 Hz, 3 H), 7.25 (d, J = 9.0 Hz, 1
H), 6.84 (d, J = 8.4 Hz, 2 H), 5.69 (s, 1 H), 4.40 (br. s, 1 H), 4.20
(dd, J = 8.7, 4.5 Hz, 1 H), 4.02 (m, 1 H), 3.77 (dd, J = 11.7, 3.0 Hz,
1 H), 3.71 (dd, J = 11.7, 5.1 Hz, 1 H), 2.96 (br. s, 6 H) ppm. 13C
NMR (75 MHz, CD3OD): δ = 180.0, 155.0, 152.3, 150.6, 144.4,
131.1, 125.6, 122.1, 116.7, 124.0, 112.1, 109.1, 88.3, 83.0, 79.0, 63.4,
41.1 ppm. MS (ESI): m/z = 430.0 [M + H]+. HRMS (ESI): calcd.
for C22H23O8NNa+ 452.1316; found 452.1320.
+
C21H21O9 417.1180; found 417.1190.
5,7-Dihydroxy-3Ј-methoxyisoflavone
7-O-α-D-Arabinofuranoside
(23d): Yield: 20 mg, 37%, procedure A. Rf = 0.47 (CH2Cl2/MeOH,
10:1). [α]2D4 = 89.2 (c = 0.08, MeOH). 1H NMR (300 MHz,
CD3OD): δ = 8.22 (br. s, 1 H), 7.34 (t, J = 7.5 Hz, 1 H), 7.15 (br.
s, 1 H), 7.11 (d, J = 7.5 Hz, 1 H), 6.96 (d, J = 7.5 Hz, 1 H), 6.70
(d, J = 1.5 Hz, 1 H), 6.51 (d, J = 1.5 Hz, 1 H), 5.65 (br. s, 1 H),
4.29 (d, J = 3.6 Hz, 1 H), 4.10–3.98 (m, 2 H), 3.82 (s, 3 H), 3.78
(dd, J = 12.0, 3.0 Hz, 1 H), 3.70 (dd, J = 12.0, 4.5 Hz) ppm. MS
(ESI): m/z = 417.2 [M + H]+, 439.2 [M + Na]+. HRMS (ESI):
4Ј-tert-Butoxycarbonylamino-7,8-dihydroxyisoflavone 7-O-α-D-Ara-
binofuranoside (22l): Yield: 25 mg, 39%. Rf = 0.42 (CHCl3/MeOH,
10:1). [α]2D4 = 45.6 (c = 0.10, MeOH). 1H NMR (300 MHz,
CD3OD): δ = 8.57 (s, 1 H), 8.28 (s, 1 H), 7.60 (d, J = 9.0 Hz, 1 H),
+
calcd. for C21H21O9 417.1180; found 417.1178.
3162
www.eurjoc.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2008, 3156–3163