1
782
F. Zhu et al.
LETTER
1
08.3, 115.4, 122.0, 125.9, 136.0, 146.1, 148.0, 148.6,
OCH ), 4.08 (q, J = 6.9 Hz, 4 H, CH CH ), 5.87 (s, 2 H,
3 2 3
+
OH), 6.43 (s, 2 H, H-2, H-2¢), 6.65 (s, 2 H, H-6, H-6¢). 13C
168.5. MS (EI): m/z (%) = 250(8) [M ], 235 (100) [M –
+
CH ] . HRMS (EI): m/z calcd for C H O + H: 251.1278;
found: 251.1281.
NMR (75 MHz, CDCl ): d = 14.1, 29.3, 34.5, 35.7, 48.1,
3
14 18
4
3
55.9, 60.5, 108.8, 119.7, 128.2, 134.6, 142.6, 146.4, 173.7.
+
(
9) Rosenwald, H. R. J. Am. Chem. Soc. 1952, 74, 4602.
MS (EI): m/z (%) = 558 (14) [M ], 279 (10), 193 (88), 149
(
(
10) Coffield, T. H.; Filbey, A. H.; Ecke, G. G.; Kolka, A. J. J.
Am. Chem. Soc. 1957, 79, 5019.
(100). HRMS (EI): m/z calcd for C H O + H: 559.3265;
3
2
46
8
found: 559.3267.
(16) Compound 11: colorless oil. IR (neat): 3429, 2934, 1727,
11) Compound 7: white solid; mp 218–220 °C. IR (neat): 3391,
–
1
1
–1 1
2
950, 1753, 1693, 1652, 1151 cm . H NMR (300 MHz,
1516 cm . H NMR (300 MHz, CDCl ): d = 1.21 (t, J = 7.2
3
acetone-d ): d = 1.40 (s, 18 H, CH ), 3.88 (s, 6 H, OCH ),
Hz, 6 H, CH CH ), 2.83–2.86 (m, 2 H CH), 2.91–2.96 (m, 4
6
3
3
2
3
4
.11 (d, J = 1.2 Hz, 2 H, H-1, -5), 5.79 (br s, 4 H, H-2, H-6),
H, ArCH ), 3.78 (s, 6 H, OCH ), 4.10 (q, J = 7.2 Hz, 4 H,
2
3
1
3
6
.96 (s, 2 H, H-2¢, H-2¢¢), 6.97 (s, 2 H, H-6¢, H-6¢¢). C NMR
CH CH ), 5.49 (s, 2 H, OH), 6.48 (s, 2 H, H-2, H-2¢), 6.59
2 3
(
(
(
-
(
75 MHz, acetone-d ): d = 29.5 (CH ), 35.0 (CMe ), 48.9
(d, J = 8.1 Hz, 2 H, H-6, H-6¢), 6.79 (d, J = 8.1 Hz, 2 H, H-
6
3
3
1
3
C-1, 5), 56.3 (OCH ), 83.4 (C-2,6), 107.1 (C-2¢, -2¢¢), 117.3
5, H-5¢). C NMR (75 MHz, CDCl ): d = 14.1, 35.3, 47.5,
3
3
C-6¢, -6¢¢), 129.1 (C-1¢, -1¢¢), 135.9 (C-5¢, -5¢¢), 145.9 (C-4¢,
4¢¢), 148.3 (C-3¢, -3¢¢), 175.8 (C=O). MS (EI): m/z (%) = 498
55.6, 60.6, 112.2, 114.0, 121.9, 130.5, 144.1, 146.3, 179.5.
MS (EI): m/z (%) = 446 (10) [M ], 277 (31), 223 (24), 177
+
+
+
62) [M ], 483 (40) [M – CH ] , 57 (100). HRMS (EI):
(28), 149 (53), 137 (100). HRMS (EI): m/z calcd for
3
m/z calcd for C H O + H: 499.2326; found: 499.2328.
C H O + H: 447.2013; found: 447.2021.
2
8
34
8
24 30
8
(
12) Compound 8: white solid; mp 199–200 °C. IR (neat): 3525,
(17) (±)-Matairesinol (1): pale yellow solid; mp 66–67 °C. IR
–
1
1
–1 1
2955, 1701, 1593, 1297 cm . H NMR (300 MHz, acetone-
(neat): 3418, 2935, 1760, 1606, 1239 cm . H NMR (300
d ): d = 1.34 (s, 18 H, CH ), 2.74–2.79 (m, 2 H, CH), 2.86–
MHz, CDCl ): d = 2.40–2.63 (m, 4 H, H-7, H-8, H-8¢), 2.87
6
3
3
3.01 (m, 4 H, ArCH ), 3.73 (s, 6 H, OCH ), 6.68 (br s, 4 H,
(dd, J = 14.2, 6.8 Hz, 1 H, H-7¢), 2.95 (dd, J = 14.2, 5.2 Hz,
2
3
1
3
H-2, H-2¢, H-6, H-6¢). C NMR (75 MHz, acetone-d6):
1 H, H-7¢), 3.80 (s, 6 H, OCH ), 3.89 (dd, J = 9.2, 7.2 Hz, 1
3
d = 29.9, 35.1, 37.7, 50.8, 56.4, 110.8, 120.1, 130.4, 135.3,
H, H-9), 4.15 (dd, J = 8.8, 7.2 Hz, 1 H, H-9), 5.64 (br s, 2 H,
OH), 6.40 (d, J = 1.6 Hz,1 H, H-2), 6.50 (dd, J = 8.0, 2.0 Hz,
1 H, H-6), 6.59 (dd, J = 8.0, 2.0 Hz, 1 H, H-6¢), 6.60 (br s, 1
H, H-2¢), 6.79 (d, J = 8.4 Hz,1 H, H-5), 6.81 (d, J = 8.4Hz, 1
+
1
43.6, 147.7, 178.3. EIMS: m/z (%) = 484 (10) [M – 18] ,
2
27 (10), 193 (100). HRMS (EI): m/z calcd for C H O +
2
8
38
8
Na: 525.2459; found: 525.2454.
1
3
(
13) Compound 9: pale yellow gum. IR (neat): 3524, 2955, 1767,
H, H-5¢). C NMR (75 MHz, DMSO-d ): d = 33.7, 36.9,
6
–
1 1
1
9
595, 1232 cm . H NMR (300 MHz, CDCl ): d = 1.36 (s,
40.9, 45.7, 55.4, 55.5, 70.8, 112.6, 113.4, 115.4, 120.7,
120.6, 128.9, 129.7, 144.9, 145.1, 147.4, 147.5, 178.6. MS
(EI): m/z (%) = 358 (4) [M ], 137 (100). HRMS (EI): m/z
3
H, CH ), 1.39 (s, 9 H, CH ), 2.40–2.70 (m, 4 H, H-7¢, H-8,
3
3
+
H-8¢), 2.91 (dd, J = 14.0, 6.3 Hz, 1 H, H-7), 3.03 (dd,
J = 14.0, 4.8 Hz, 1 H, H-7), 3.79 (s, 3 H, OCH ), 3.82 (s, 3
calcd for C H O + NH : 376.1755; found: 376.1754.
3
20 22
6
4
H, OCH ), 3.88 (dd, J = 9.3, 6.6 Hz, 1 H, H-9¢,), 3.96 (dd,
(18) (±)-Secoisolariciresinol (2): white solid; mp 116–117 °C. IR
3
–
1 1
J = 9.0, 6.6 Hz, 1 H, H-9¢), 5.89 (s, 1 H, OH), 5.91 (s, 1 H,
OH), 6.33 (d, J = 1.2 Hz, 1 H, H-2¢), 6.54 (d, J = 1.2 Hz, 1
H, H-2), 6.59 (d, J = 1.2 Hz, 1 H, H-6¢), 6.69 (br s, 1 H, H-
(neat): 3351, 2933, 1515 cm . H NMR (300 MHz, CDCl ):
3
d = 1.85 (br s, 2 H, H-8, H-8¢), 2.64 (dd, J = 13.5, 6.9 Hz, 2
H, H-7, H-7¢), 2.74 (dd, J = 13.5, 8.1 Hz, 2 H, H-7, H-7¢),
3.54 (dd, J = 12, 4.2 Hz, 2 H, H-9, H-9¢), 3.78–3.85 (m, 2 H,
1
3
6
3
1
1
). C NMR (75 MHz, CDCl ): d = 29.6, 29.7, 34.8, 35.2,
3
8.9, 41.3, 47.1, 56.3, 71.6, 108.7, 109.5, 119.3, 120.1,
28.1, 128.3, 135.5, 135.8, 143.1, 143.2, 146.8, 147.0,
79.2. MS (EI): m/z (%) = 470 (8) [M ], 193 (100). HRMS
H-9, H-9¢), 3.81 (s, 6 H, OCH ), 6.58 (s, 2 H, H-2, H-2¢), 6.62
3
(d, J = 8.4 Hz, 2 H, H-6, H-6¢), 6.80 (d, J = 8.4 Hz, 2 H, H-
+
13
5, H-5¢). C NMR (75 MHz, CDCl ): d = 35.9, 43.8, 55.8,
3
(
EI): m/z calcd for C H O + NH : 488.3007; found:
60.8, 111.4, 114.1, 121.7, 132.4, 143.8, 146.4. MS (EI): m/z
(%) = 362 (11) [M ], 277 (6), 189 (6), 137 (100). HRMS
2
8
38
6
4
+
488.3009.
(
(
14) Tashiro, M.; Yamato, T. J. Org. Chem. 1979, 44, 3037.
15) Compound 10: colorless oil. IR(neat): 3526, 2956, 1730,
(EI): m/z calcd for C H O + NH : 380.2068; found:
380.2061.
(19) Ahmed, R.; Lehrer, M.; Stevenson, R. Tetrahedron 1973,
29, 3753.
2
0
26
6
4
–
1 1
1
595, 1372 cm . H NMR (300 MHz, CDCl ): d = 1.18 (t,
3
J = 6.9 Hz, 6 H, CH CH ), 1.36 (s, 18 H, CH ), 2.86–2.89
2
3
3
(
m, 2 H, CH), 2.90–2.96 (m, 4 H, ArCH ), 3.77 (s, 6 H,
2
Synlett 2006, No. 11, 1780–1782 © Thieme Stuttgart · New York