936
T. da Silva, L.M.X. Lopes / Phytochemistry 67 (2006) 929–937
(d, C-3), 147.6 (s, C-4), 147.5 (s, C-5), 109.1 (d, C-6), 121.1
(d, C-7), 138.8 (s, C-8), 22.1 (q, C-9), 138.2 (s, C-10), 111.1
(d, C-20), 148.7 (s, C-30), 147.8 (s, C-40), 111.0 (d, C-50),
119.6 (d, C-60), 50.9 (d, C-70), 42.0 (d, C-80), 18.7 (q, C-
90), 55.8 (2 · q, OCH3-30,4), 2 · 55.9 (2 · q, OCH3-40,5)
(13C NMR data agree with those reported in the literature
(Fonseca et al., 1979) except for assignments of several car-
C-20), 149.5, (s, C-30), 148.0 (s, C-40), 111.6 (d, C-50), 122.5
(d, C-60), 53.5 (d, C-70), 41.5 (d, C-80), 15.6 (q, C-90), 3 · 55.8
(3 · q, OCH3-30,40,5), 55.3 (q, OCH3-4); for 1H NMR spec-
tra, see Table 4; CD (MeOH; c 0.1): [h]220 0, [h]221 ꢀ792;
[h]225 ꢀ627, [h]236 ꢀ6699, [h]254 ꢀ1122, [h]276 ꢀ4422, [h]282
0, [h]288 +3630, [h]296 0, [h]300 ꢀ1452.
Treatment of 11 (38.0 mg) and 13 (28.0 mg) with LiAlH4
(97.0 mg) in THF (1 ml), according to the reduction proce-
dure described previously, gave 5b (34.7 mg) and 5c
(23.9 mg), respectively.
1
bons that should be interchanged); for H NMR spectra,
see Table 5; CD (MeOH; c 0.1): [h]225 +990, [h]227 +1320;
[h]231 0, [h]237 ꢀ1650, [h]259 ꢀ330, [h]271 ꢀ3960, [h]290
ꢀ1254, [h]300 ꢀ1303; positive APCI-MS (probe) 20 eV m/
z (rel. int.): 355 [M+H]+ (5), 219 (100), 149 (20), 121
(18). Found: C, 74.6; H, 7.4. C22H26O4 requires: C, 74.6;
H, 7.4%.
4.4.2. (7R,70R,8S,80R)-30,40,4,5-Tetramethoxy-2,70-
cyclolignan-7-ol [(ꢀ)-aristoligol, 5b]
25
Amorphous yellow solid; ½aꢂD ꢀ 106:5ꢃ (CHCl3; c 1.8),
lit. 167.0ꢁ (CHCl3; c 2.2); IR (KBr) mmax 3458, 2937, 1604,
1
4.3.7. Wulignan A2 (8)
1510 cmꢀ1; for H NMR spectra, see Table 4; 13C NMR
25
Amorphous yellow solid; ½aꢂD ꢀ 55:0ꢃ (CHCl3; c 0.90),
(126 MHz, CDCl3): d 130.1 (s, C-1), 132.1 (s, C-2), 111.7
(d, C-3), 147.9 (s, C-4), 147.8 (s, C-5), 109.2 (d, C-6), 75.9
(d, C-7), 37.6 (d, C-8), 15.8 (q, C-9), 134.9 (s, C-10), 114.1
(d, C-20), 147.5 (s, C-30), 147.3 (s, C-40), 110.3 (d, C-50),
122.7 (d, C-60), 50.5 (d, C-70), 37.4 (d, C-80), 17.5 (q, C-90),
4 · 55.9 (4 · q, OCH3-30,40,4,5); CD (MeOH; c 0.1) [h]214
0, [h]222 +7260, [h]227 0, [h]239 ꢀ35,640, [h]253 ꢀ990, [h]273
ꢀ15,840, [h]286 0, [h]289 +1320, [h]293 0, [h]295 ꢀ990, compa-
rable to the literature (Urzu´a and Shamma, 1988).
14
1
[lit. ½aꢂD ꢀ 61:2ꢃ (CHCl3; c 0.17) (Jia-Sen et al., 1988)]; H
NMR, UV, IR, and CD data agree with those reported
in the literature (Jia-Sen et al., 1988); 13C NMR
(126 MHz, CDCl3): d 125.2 (s, C-1), 140.0 (s, C-2), 115.4
(d, C-3), 150.7 (s, C-4), 145.8 (s, C-5), 108.9 (d, C-6),
200.2 (s, C-7), 41.0 (d, C-8), 11.7 (q, C-9), 135.5 (s, C-10),
111.9 (d, C-20), 146.7 (s, C-30), 144.4 (s, C-40), 114.2 (d,
C-50), 121.9 (d, C-60), 49.8 (d, C-70), 42.0 (d, C-80), 16.0
(q, C-90), 55.9 (q, OCH3-30), 56.1 (q, OCH3-5).
4.4.3. (7S,70R,8S,80S)-30,40,4,5-Tetramethoxy-2,70-
4.3.8. Epischisandrone (9)
cyclolignan-7-ol [(ꢀ)-holostylol C, 5c]
;
(KBr) mmax 3402, 2959, 1602, 1512 cmꢀ1 13C NMR
25
25
Amorphous yellow solid; ½aꢂD ꢀ 24:0ꢃ (CHCl3; c 1.25),
Amorphous yellow solid; ½aꢂD ꢀ 20:0ꢃ (CHCl3; c 1.6); IR
14
1
[lit. ½aꢂD þ 5:50ꢃ (CHCl3; c 1.05) (Jia-Sen et al., 1988)]; H
NMR, UV, IR, and CD data agree with those reported
in the literature (Jia-Sen et al., 1988); 13C NMR
(126 MHz, CDCl3): d 126.4 (s, C-1), 137.8 (s, C-2), 111.3
(d, C-3), 151.3 (s, C-4), 144.7 (s, C-5), 111.9 (d, C-6),
200.0 (s, C-7), 42.6 (d, C-8), 11.9 (q, C-9), 136.5 (s, C-10),
112.0 (d, C-20), 149.1 (s, C-30), 147.3 (s, C-40), 111.1 (d,
C-50), 121.4 (d, C-60), 50.5 (d, C-70), 42.5 (d, C-80), 15.9
(q, C-90), 55.9 (q, OCH3-30), 2 · 56.0 (2 · q, OCH3-40,5).
(126 MHz, CDCl3): d 130.6 (s, C-1), 131.3 (s, C-2), 112.0
(d, C-3), 147.7 (s, C-4), 147.3, 147.9, (2 · s, C-40,5), 108.5
(d, C-6), 72.5 (d, C-7), 39.9 (d, C-8), 6.6 (q, C-9), 138.2 (s,
C-10), 112.2 (d, C-20), 148.8 (s, C-30), 110.8 (d, C-50),
121.6 (d, C-60), 49.3 (d, C-70), 39.4 (d, C-80), 17.7 (q, C-
1
90), 4 · 55.7 (4 · q, OCH3-30,40,4,5); for H NMR spectra,
see Table 4; CD (MeOH; c 0.1): [h]222 +7260, [h]229 0,
[h]239 ꢀ28,710, [h]251 ꢀ990, [h]283 ꢀ1584, [h]289 +1320,
[h]293 0, [h]299 ꢀ990.
4.4. Chemical transformations
Solutions of 5b (18.6 mg) and 5c (17.7 mg) in dry C6H6
(5 ml) and PTSA (8.8 mg) were individually stirred at room
temp. for 1 h under N2 atmosphere. The solutions were
then washed with aqueous saturated NaHCO3 solution,
extracted with C6H6, and then dried (MgSO4), filtered
and evaporated. The resulting organic residues were char-
acterized as 6 (14.5 mg) and 6a (13.9 mg), respectively.
A solution of 12 (5.2 mg) in dry THF was added drop-
wise to a suspension of LiAlH4 (48.5 mg) in THF
(0.5 ml). The mixture was then stirred (30 min), treated
with THF saturated with H2O until H2 ceased to evolve,
and then with aqueous saturated NH4Cl solution. The
solution was extracted with CHCl3 (4 · 2 ml), and the
organic solutions were combined, dried (MgSO4), and
evaporated. The residue (4.6 mg) was characterized as 5a.
4.4.4. (70R,80R)-30,40,4,5-Tetramethoxy-2,70-cyclolignan-7-
ene [(+)-70-epi-cyclogalgravin, 6a]
25
Amorphous yellow solid; ½aꢂD þ 57:0ꢃ (CHCl3; c 1.3); IR
4.4.1. (7S,70R,8R,80S)-30,40,4,5-Tetramethoxy-2,70-
(KBr) mmax 2923, 1600, 1510 cmꢀ1 13C NMR (126 MHz,
;
cyclolignan-7-ol [(ꢀ)-holostylol B, 5a]
;
IR (KBr) mmax 3409, 2972, 1618, 1512 cmꢀ1 13C NMR
(126 MHz, MeOH-d4): d 132.8 (s, C-1), (C-2, not observed),
112.4 (d, C-3), 147.5, 147.4, (2 s, C-4,5), 109.7 (d, C-6), 74.1
(d, C-7), 44.0 (d, C-8), 14.6 (q, C-9), 139.0 (s, C-10), 112.8 (d,
CDCl3): d 147.1, 147.4, 147.6, 148.3 (4 · s, C-30,40,4,5),
140.2 (s, C-8), 133.6 (s, C-10), 127.8, 128.4 (2 · s, C-1,2),
122.1 (d, C-7), 121.8 (d, C-60), 113.2, 111.6, 110.8, 109.2
(4 · d, C-3,6,20,50), 4 · 55.9 (4 · q, OCH3-30,40,4,5), 50.0
(d, C-70), 39.5 (d, C-80), 21.4 (q, C-9), 13.1 (q, C-90); for
1H NMR spectra, see Table 5; CD (MeOH; c 0.1): [h]230
25
Amorphous yellow solid; ½aꢂD ꢀ 35:0ꢃ (CHCl3; c 0.75);