- Email: [email protected]
Congeners of norditerpene dilactones from Podocarpus nagi
Short Reports radiation with graphite-monochromated and 1502 independence reflections were recorded; 1390 with 183~~ (I) were considered as observed. The molecular structure was solved by direct method (SHELXTL program). Twenty-three non-hydrogen atoms were located from E map. Least-squares refinement and Fouriers synthesis gave the coordinate of all non-
hydrogen
3953 atoms,
R=0.0444.
The
M., Tanaka,
is
T., Iinuma,
M., Xu, G. and
Phytochemistry 28, 553.
Vol. 29, No. 12, pp. 3953-3955,1990 Printed in Great Britain.
OF
formula
REFERENCE
1. Min, Z., Mizuno, Huang, Q. (1989)
Phytochemistry,
CONGENERS
molecular
CHO 20 28 3’
0031-9422/90$3.00+0.00 0 1990Pergamon Press plc
NORDITERPENE
DILACTONES NAGI
FROM
PODOCARPUS
BAI-PING YING, IsA0 KUBO,* CHAIRUL,? TAKESHI MATSUMOTOt and YUJI HAYASHI*t Division of Entomology and Parasitology, College of Natural Resources, University of California Berkeley, CA 94720, U.S.A.; tFaculty of Science, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan
(Received12 March 1990) Key Word Index-Podocarpus nagi; Podocarpaceae; root bark; norditerpene dilactone; 2,3-dehydro-16hydroxynagilactone F; nagilactone I; 16-hydroxynagilactone E.
Abstract-Three new norditerpene dilactones, 2,3-dehydro-16-hydroxynagilactone F, nagilactone I and ldhydroxynagilactone E were isolated from the root bark of Podocarpus nugi. Their structures were established on the basis of the spectroscopic analyses.
INTRODUCTION Many
biologically
active
norditerpene
dilactones
have
been isolated from various species of Podocarpus plants (Podocarpaceae) [14]. In particular, seeds and root bark of P. nagi were found to be rich sources of the dilactones. Norditerpene dilactones possess various biological activities such as anti-tumour [S, 61, plant growth regulatory [7, S] and insecticidal [9, lo] activities, and antifeedant activity against herbivorous animals [ll]. In our continuing search for bioactive substances from P. nagi, three new norditerpene dilactones were isolated. RESULTS AND DISCUSSION All three new components, compound 1-3, showed 19 skeletal carbon signals in their “CNMR spectra (Table l), including those of two types of lactone carbonyl carbons at 6 163-164 and 177-182. The compounds 1 and 2 give a characteristic electronic transition at 262-263 nm due to a dienolide system on the B/C ring (type C
dilactones) Cl], and compound 3 showed a transition at 220 nm, typical for a epoxyenolide system (type B dilactones) [l].
*Authors PHYTO29:12-R
to whom correspondence
should
be addressed.
Compound 1 has a molecular formula C,,H,,O, by high resolution mass spectrometry. The ‘HNMR spectrum showed typical splitting modes of the y-lactone ring protons over the A/B ring system (5-H at 6 1.95 and 6-H at 65.06) and two olefinic protons (7-H at 66.51 and 11-H at 65.92) and a carbinyl proton (14-H at 65.15) of the dienolide system on B/C ring with a-oriented side chain at C-14 [ll]. Two other olefinic protons at 65.8-5.9, coupled to each other, indicate an additional double bond on the ring A. Two carbinyl protons (at 63.93 and 4.14) suggest the presence of a primary carbinol group, which should be placed on the C-14 side chain (at C-16). The whole structure of compound 1 was finally derived by careful comparison of its 13CNMR data with those of previously known dilactones [12] (Table 1). The position of the ring A double bond (A’*‘) and partial structure of the C-14 side chain are supported by comparison with 16hydroxypodolide (6) [13]. The dienolide system on the B/C ring is confirmed from comparison with nagilactone F (4) [14] and 3-hydroxynagilactone F (5) [15]. Thus, compound 1 is 2,3-dehydro-16-hydroxynagilactone F. Compound 2 has a molecular formula C2,,Hz40, (HRMS). The presence of a methoxycarbonyl group is shown by a three-proton singlet at 63.63 and an additional carbonyl carbon at 6 172.6. A three-proton doublet at 6 1.46 (H,-17) indicates that the methoxycarbonyl group is located at the C-15 position. A secondary
Short Reports
3954
hydroxyl group is placed at the 2a-position on the ring A, as the signal of the corresponding carbinyl proton (axial) appeared at 64.28 as a very broad signal ( W1,2= 28 Hz). The 13C NMR data also support the 2-hydroxy structure, because the chemical shifts of the ring A carbons are consistent with those of I-deoxy-2~hydroxynagilactone A (7) [ 161. The dienolide system on the B/C-rings is also shown by correlation with the dilactones 4 and 5. Therefore, the structure of compound 2 is assigned as the methyl ester of 2cr-hydroxynagilactone F 16-oic acid and it is named as nagilactone 1. Compound 3, C,9H2407, showed signals of two types of alcoholic carbinyl protons (63.84, lH, and 64.08 and 4.31, each 1H: AB part of an ABX system). The 13C NMR spectral properties are very similar to those of nagilactone E (8) [14] (for ring system) and 16-hydroxypodolide (6) (for C-14 side chain). Therefore, the structure of 16hydroxynagilactone E is assigned as compound 3. The configuration at C-15 of the three compounds remains undetermined.
4 R=H 5 R=OH
1
0
0
EXPERIMENTAL General. Mps: uncorr. UV spectra were recorded in MeOH. ‘H and ‘%NMR spectra were measured in CDCI, or pyridined, with TMS as int. standard at 400 or 100 MHz (‘H) and 100 or 25 MHz (I%), respectively. Mass spectra were determined by a JEOL D-300 spectrometer with El mode at 30 eV. Separation of compounds. The root bark of Podocarpus nagi (Thunberg) Pilger was collected at Nara, Japan. The mother liquor of the nagilactones remaining from our previous work was re-chromatographed repeatedly on a silica gel (4&63 pm) column, eluted with CHCl,-Me,CO (4: 1) and (3: I), to give 271 mg 1, 412 mg 2 and 127 mg 3.
0
Table 1*
C 1 2 3 4 5 6 7 8 9 10 11 12 14 15 16 17 18 19 20 OMe
33.2 126.5 128.1 44.7 47.1 71.1 122.3 134.0 158.5 35.0 111.8 163.8 82.1 37.0 63.3 15.0 23.3 178.3 22.5
2t (2) (1) (1) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (2) (3) (3) (0) (3)
*In chloroform-d. tin pyridine-d,.
41.0 63.9 37.6 42.8 45.3 72.4 122.5 133.2 158.8 36.2 113.1 163.5 80.0 42.4 172.6 13.8 28.0 181.6 23.3 51.9
1. “CNMR
4*
3P (2) (1) (2) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (0) (3) (3) (0) (3) (3)
29.3 28.5 72.9 45.6 45.3 72.4 54.9 58.9 159.4 36.6 116.7 163.9 82.4 34.6 62.5 16.0 23.9 177.8 21.9
spectra
(2) (2) (1) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (2) (3) (3) (0) (3)
30.1 17.6 27.9 42.9 47.6 71.9 121.8 134.2 159.2 35.2 112.0 164.3 83.1 29.8 15.3 19.7 25.0 180.9 24.3
of the dilactones 5’
(2) (2) (2) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (3) (3) (3) (0) (3)
29.9 28.8 73.3 45.0 49.7 72.4 121.1 135.4 158.3 35.7 111.8 163.9 83.0 29.8 15.2 19.7 23.5 179.9 22.3
[12] 7t
6t (2) (2) (1) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (3) (3) (3) (0) (3)
32.5 126.5 128.3 44.2 43.2 72.2 54.7 58.1 158.4 35.6 117.5 163.7 82.3 34.5 62.5 16.1 22.8 178.0 22.5
(2) (1) (1) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (2) (3) (3) (0) (3)
44.0 64.0 37.6 43.0 48.4 75.1 60.0 111.7 169.9 37.5 106.7 162.3 166.8 29.5 20.0 20.8 27.6 182.0 24.2
a* (2) (1) (2) (0) (1) (1) (1) (0) (0) (0) (1) (0) (0) (1) (3) (3) (3) (0) (3)
28.9 28.4 73.0 44.3 45.4 73.0 53.5 58.7 158.2 36.4 116.8 163.4 82.9 26.8 16.5 21.3 24.2 179.3 21.7
(2) (2) (1) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (3) (3) (3) (0) (3)
Short Reports 2,3-Dehydro-16-hydroxynagilactone F (1). Mp 205-206” (from MeOH-CHCl,). C,,H,,O, (m/z 330.1462, talc. 330.1465). UV A”,’ nm: 262. ‘HNMR (CJXI,): 61.20 (s, 3H, 18 or 20-H,), 1.28 (d, 3H, J=6.8 Hz, 17-H,), 1.42 (s, 3H, 20 or 18-H,), 2.15 (d, lH, J=5.0 Hz, 5-H), 2.21 (d, 2H, J=2.0 Hz, l-H), 3.76 (br s, 2H, 16-H), 4.97 (q, lH, J= 1.8 Hz, 14-H), 5.10 (ddd, lH, J= 1.8, 5.0, 5.0 Hz, 6-H), 5.76 (d, lH, J= 1.8 Hz, 11-H), 5.89 (br s, 2H, 2-H and 3-H), 6.34 (ddd, J= 1.8,1.8,5.0 Hz, 7-H). Qyridine-d,) 1.16 (s, 3H, 18 or 20-H,), 1.33 (s, 3H, 20 or 18-H,), 1.39 (d, 3H, J =6.8 Hz, 17-H,), 1.95 (4 lH, J=5.1 Hz, 5-H), 2.02 (br s, 2H, lH), 2.59 (m, lH, W,,,=18.5 Hz, 15-H), 3.93 (dd, lH, J=8.1, 10.3 Hz, 16a-H), 4.14 (dd, lH, J=3.9, 10.3 Hz, 16b-H), 5.06 (tlike, HI, 6-H), 5.15 (br s, lH, 14-H), 5.82(dd, lH, J=3.8, 7.3 Hz, 2-H), 5.91 (d, lH, J=7.3 Hz, 3-H), 5.92 (s, lH, 11-H), 6.51 (br s, lH, 7-H). Nagiloctone I (2). Mp 222-224” (from MeOH-CHCI,). C,,H,,O, (m/z 376.1538, talc. 376.1523). UVI::” nm: 263. ‘HNMR (pyridine-d,): 61.30 (s, 3H, 18-H,), 1.36 (s, 3H, 20-H,), 1.46 (d, 3H, J=6.8 Hz, 17-Hs), 1.83 (d, lH, J=5.6 HZ 5-H), 1.85 (d, lH, J=12.4Hz, 38-H) 2.17 (dd, lH, J=4.9, 13.3 Hz, l/3-H),2.47(dd, lH, J=9.6, 13.3 Hz, la-H),2.54(dd, lH, J= 12.4, 13.3 Hz, 3a-H), 3.39 (dq, lH, J=3.9,6.8 Hz, 15-H) 3.63 (s, 3H, OMe), 4.28 (m, WI,, = 28 Hz, Z/?-H), 5.16 (t-like, lH, 6-H) 5.32(brs, lH, 14-H).6.09(s, lH, ll-H),6.43(d, lH, J=2.1 H&7H). 16-Hydroxynagilactone E (3). Mp 224227” (from MeOHCHCI,). C,,H,,O, (m/z 364.1528, talc. 364.1523). UV$$’ 220nm. ‘HNMR (pyridine-d,): 61.32 (s, 3H, 18-H,), 1.36 (d, 3H, J=6.5 Hz, 17-H,), 1:56 (s, 3H, 20-H,), 1.90 (d, lH, J = 5.0 Hz, 5-H), 3.84 (dd, lH, J = 7.0, 10.0 Hz, 3-H), 4.08 (dd, lH, J =7.0,10.0 Hz, 16a-H),4.31 (dd, lH, J=4.0,10.0 Hz, 16b-H),4.39 (br s, lH, 7-H), 4.88 (d, lH, J=5.5Hz, 14-H), 5.13 (br d, lH, J=5.0Hz, 6-H) 6.16(s, lH, 11-H). Acknowledgement-BPY thanks Takasago Institute for Interdisciplinary Science for a fellowship.
3955 REFERENCES
4. 5. 6. 7. 8. 9. 10. 11.
12. 13. 14. 15. 16.
Hayashi, Y. and Matsumoto, T. (1982) J. Org. Gem. 47, 3421. Watson, W. H., Zabel, V., Silva, M. and Bittner, M. (1982) Acta Cryst. B38, 588. Matlin, S. A., Prazeres, M. A., Mersh, J. D., Sanders, J. K. M., Bittner, M. and Silva, M. (1982) J. Chem. Sot. Perkin Trans I 2589. Cassady, J. M., Lightner, T. K., McCloud, T. M., Hembree, J. A., Bym, S. R. and Chang, C. (1984) J. Org. Chem. 49,942. Hayashi, Y., Matsumoto, T. and Tashiro, T. (1979) Gann 70, 365. Hembree, J. M., Chang, C., McLaughlin, J. L. and Cassady, J. M. (1980) Experientia 36, 28. Sasse, J. M. Rowanand, K. S. and Gaibraith, M. N. (1981) Phytochemistry 20, 2195. Kubo, I., Matsumoto, T., Hanke, F. J., Taniguchi, M. and Hayashi, Y. (1985) Experientia 41, 1462. Singh, P., Russell, G. M., Hayashi, Y., Gallagher, R. T. and Fredericksen, S. (1979) Entomol. Exp. Appl. 25, 121. Kubo, I., Matsumoto, T. and Klocke, J. A. (1985) J. Chem. Ecol. 10, 547. Kim, Y., Chairul and Hayashi, Y. (1989) Abstract of 58th Annual Symposium of Japan Chemical Society (Kyoto) II, 1157. Hayashi, Y., Matsumoto, T., Uemura, M. and Koreeda, M. (1980) Org. Mag. Reson. 14, 86. Hayashi, Y., Matsumoto, T., Yuki, Y. and Sakan, T. (1977) Tetrahedron Letters 4215. Hayashi, Y., Yokoi, J., Watanabe, Y. and Sakan, T. (1972) Chem. Letters 759. Hayashi, Y., Matsumoto, T. and Sakan, T. (1978) Heterocycles 10, 123. Hayashi, Y., Yuki, Y., Matsumoto, T. and Sakan, T. (1977) Tetrahedron Letters 3637.
hydrogen
3953 atoms,
R=0.0444.
The
M., Tanaka,
is
T., Iinuma,
M., Xu, G. and
Phytochemistry 28, 553.
Vol. 29, No. 12, pp. 3953-3955,1990 Printed in Great Britain.
OF
formula
REFERENCE
1. Min, Z., Mizuno, Huang, Q. (1989)
Phytochemistry,
CONGENERS
molecular
CHO 20 28 3’
0031-9422/90$3.00+0.00 0 1990Pergamon Press plc
NORDITERPENE
DILACTONES NAGI
FROM
PODOCARPUS
BAI-PING YING, IsA0 KUBO,* CHAIRUL,? TAKESHI MATSUMOTOt and YUJI HAYASHI*t Division of Entomology and Parasitology, College of Natural Resources, University of California Berkeley, CA 94720, U.S.A.; tFaculty of Science, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558, Japan
(Received12 March 1990) Key Word Index-Podocarpus nagi; Podocarpaceae; root bark; norditerpene dilactone; 2,3-dehydro-16hydroxynagilactone F; nagilactone I; 16-hydroxynagilactone E.
Abstract-Three new norditerpene dilactones, 2,3-dehydro-16-hydroxynagilactone F, nagilactone I and ldhydroxynagilactone E were isolated from the root bark of Podocarpus nugi. Their structures were established on the basis of the spectroscopic analyses.
INTRODUCTION Many
biologically
active
norditerpene
dilactones
have
been isolated from various species of Podocarpus plants (Podocarpaceae) [14]. In particular, seeds and root bark of P. nagi were found to be rich sources of the dilactones. Norditerpene dilactones possess various biological activities such as anti-tumour [S, 61, plant growth regulatory [7, S] and insecticidal [9, lo] activities, and antifeedant activity against herbivorous animals [ll]. In our continuing search for bioactive substances from P. nagi, three new norditerpene dilactones were isolated. RESULTS AND DISCUSSION All three new components, compound 1-3, showed 19 skeletal carbon signals in their “CNMR spectra (Table l), including those of two types of lactone carbonyl carbons at 6 163-164 and 177-182. The compounds 1 and 2 give a characteristic electronic transition at 262-263 nm due to a dienolide system on the B/C ring (type C
dilactones) Cl], and compound 3 showed a transition at 220 nm, typical for a epoxyenolide system (type B dilactones) [l].
*Authors PHYTO29:12-R
to whom correspondence
should
be addressed.
Compound 1 has a molecular formula C,,H,,O, by high resolution mass spectrometry. The ‘HNMR spectrum showed typical splitting modes of the y-lactone ring protons over the A/B ring system (5-H at 6 1.95 and 6-H at 65.06) and two olefinic protons (7-H at 66.51 and 11-H at 65.92) and a carbinyl proton (14-H at 65.15) of the dienolide system on B/C ring with a-oriented side chain at C-14 [ll]. Two other olefinic protons at 65.8-5.9, coupled to each other, indicate an additional double bond on the ring A. Two carbinyl protons (at 63.93 and 4.14) suggest the presence of a primary carbinol group, which should be placed on the C-14 side chain (at C-16). The whole structure of compound 1 was finally derived by careful comparison of its 13CNMR data with those of previously known dilactones [12] (Table 1). The position of the ring A double bond (A’*‘) and partial structure of the C-14 side chain are supported by comparison with 16hydroxypodolide (6) [13]. The dienolide system on the B/C ring is confirmed from comparison with nagilactone F (4) [14] and 3-hydroxynagilactone F (5) [15]. Thus, compound 1 is 2,3-dehydro-16-hydroxynagilactone F. Compound 2 has a molecular formula C2,,Hz40, (HRMS). The presence of a methoxycarbonyl group is shown by a three-proton singlet at 63.63 and an additional carbonyl carbon at 6 172.6. A three-proton doublet at 6 1.46 (H,-17) indicates that the methoxycarbonyl group is located at the C-15 position. A secondary
Short Reports
3954
hydroxyl group is placed at the 2a-position on the ring A, as the signal of the corresponding carbinyl proton (axial) appeared at 64.28 as a very broad signal ( W1,2= 28 Hz). The 13C NMR data also support the 2-hydroxy structure, because the chemical shifts of the ring A carbons are consistent with those of I-deoxy-2~hydroxynagilactone A (7) [ 161. The dienolide system on the B/C-rings is also shown by correlation with the dilactones 4 and 5. Therefore, the structure of compound 2 is assigned as the methyl ester of 2cr-hydroxynagilactone F 16-oic acid and it is named as nagilactone 1. Compound 3, C,9H2407, showed signals of two types of alcoholic carbinyl protons (63.84, lH, and 64.08 and 4.31, each 1H: AB part of an ABX system). The 13C NMR spectral properties are very similar to those of nagilactone E (8) [14] (for ring system) and 16-hydroxypodolide (6) (for C-14 side chain). Therefore, the structure of 16hydroxynagilactone E is assigned as compound 3. The configuration at C-15 of the three compounds remains undetermined.
4 R=H 5 R=OH
1
0
0
EXPERIMENTAL General. Mps: uncorr. UV spectra were recorded in MeOH. ‘H and ‘%NMR spectra were measured in CDCI, or pyridined, with TMS as int. standard at 400 or 100 MHz (‘H) and 100 or 25 MHz (I%), respectively. Mass spectra were determined by a JEOL D-300 spectrometer with El mode at 30 eV. Separation of compounds. The root bark of Podocarpus nagi (Thunberg) Pilger was collected at Nara, Japan. The mother liquor of the nagilactones remaining from our previous work was re-chromatographed repeatedly on a silica gel (4&63 pm) column, eluted with CHCl,-Me,CO (4: 1) and (3: I), to give 271 mg 1, 412 mg 2 and 127 mg 3.
0
Table 1*
C 1 2 3 4 5 6 7 8 9 10 11 12 14 15 16 17 18 19 20 OMe
33.2 126.5 128.1 44.7 47.1 71.1 122.3 134.0 158.5 35.0 111.8 163.8 82.1 37.0 63.3 15.0 23.3 178.3 22.5
2t (2) (1) (1) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (2) (3) (3) (0) (3)
*In chloroform-d. tin pyridine-d,.
41.0 63.9 37.6 42.8 45.3 72.4 122.5 133.2 158.8 36.2 113.1 163.5 80.0 42.4 172.6 13.8 28.0 181.6 23.3 51.9
1. “CNMR
4*
3P (2) (1) (2) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (0) (3) (3) (0) (3) (3)
29.3 28.5 72.9 45.6 45.3 72.4 54.9 58.9 159.4 36.6 116.7 163.9 82.4 34.6 62.5 16.0 23.9 177.8 21.9
spectra
(2) (2) (1) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (2) (3) (3) (0) (3)
30.1 17.6 27.9 42.9 47.6 71.9 121.8 134.2 159.2 35.2 112.0 164.3 83.1 29.8 15.3 19.7 25.0 180.9 24.3
of the dilactones 5’
(2) (2) (2) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (3) (3) (3) (0) (3)
29.9 28.8 73.3 45.0 49.7 72.4 121.1 135.4 158.3 35.7 111.8 163.9 83.0 29.8 15.2 19.7 23.5 179.9 22.3
[12] 7t
6t (2) (2) (1) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (3) (3) (3) (0) (3)
32.5 126.5 128.3 44.2 43.2 72.2 54.7 58.1 158.4 35.6 117.5 163.7 82.3 34.5 62.5 16.1 22.8 178.0 22.5
(2) (1) (1) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (2) (3) (3) (0) (3)
44.0 64.0 37.6 43.0 48.4 75.1 60.0 111.7 169.9 37.5 106.7 162.3 166.8 29.5 20.0 20.8 27.6 182.0 24.2
a* (2) (1) (2) (0) (1) (1) (1) (0) (0) (0) (1) (0) (0) (1) (3) (3) (3) (0) (3)
28.9 28.4 73.0 44.3 45.4 73.0 53.5 58.7 158.2 36.4 116.8 163.4 82.9 26.8 16.5 21.3 24.2 179.3 21.7
(2) (2) (1) (0) (1) (1) (1) (0) (0) (0) (1) (0) (1) (1) (3) (3) (3) (0) (3)
Short Reports 2,3-Dehydro-16-hydroxynagilactone F (1). Mp 205-206” (from MeOH-CHCl,). C,,H,,O, (m/z 330.1462, talc. 330.1465). UV A”,’ nm: 262. ‘HNMR (CJXI,): 61.20 (s, 3H, 18 or 20-H,), 1.28 (d, 3H, J=6.8 Hz, 17-H,), 1.42 (s, 3H, 20 or 18-H,), 2.15 (d, lH, J=5.0 Hz, 5-H), 2.21 (d, 2H, J=2.0 Hz, l-H), 3.76 (br s, 2H, 16-H), 4.97 (q, lH, J= 1.8 Hz, 14-H), 5.10 (ddd, lH, J= 1.8, 5.0, 5.0 Hz, 6-H), 5.76 (d, lH, J= 1.8 Hz, 11-H), 5.89 (br s, 2H, 2-H and 3-H), 6.34 (ddd, J= 1.8,1.8,5.0 Hz, 7-H). Qyridine-d,) 1.16 (s, 3H, 18 or 20-H,), 1.33 (s, 3H, 20 or 18-H,), 1.39 (d, 3H, J =6.8 Hz, 17-H,), 1.95 (4 lH, J=5.1 Hz, 5-H), 2.02 (br s, 2H, lH), 2.59 (m, lH, W,,,=18.5 Hz, 15-H), 3.93 (dd, lH, J=8.1, 10.3 Hz, 16a-H), 4.14 (dd, lH, J=3.9, 10.3 Hz, 16b-H), 5.06 (tlike, HI, 6-H), 5.15 (br s, lH, 14-H), 5.82(dd, lH, J=3.8, 7.3 Hz, 2-H), 5.91 (d, lH, J=7.3 Hz, 3-H), 5.92 (s, lH, 11-H), 6.51 (br s, lH, 7-H). Nagiloctone I (2). Mp 222-224” (from MeOH-CHCI,). C,,H,,O, (m/z 376.1538, talc. 376.1523). UVI::” nm: 263. ‘HNMR (pyridine-d,): 61.30 (s, 3H, 18-H,), 1.36 (s, 3H, 20-H,), 1.46 (d, 3H, J=6.8 Hz, 17-Hs), 1.83 (d, lH, J=5.6 HZ 5-H), 1.85 (d, lH, J=12.4Hz, 38-H) 2.17 (dd, lH, J=4.9, 13.3 Hz, l/3-H),2.47(dd, lH, J=9.6, 13.3 Hz, la-H),2.54(dd, lH, J= 12.4, 13.3 Hz, 3a-H), 3.39 (dq, lH, J=3.9,6.8 Hz, 15-H) 3.63 (s, 3H, OMe), 4.28 (m, WI,, = 28 Hz, Z/?-H), 5.16 (t-like, lH, 6-H) 5.32(brs, lH, 14-H).6.09(s, lH, ll-H),6.43(d, lH, J=2.1 H&7H). 16-Hydroxynagilactone E (3). Mp 224227” (from MeOHCHCI,). C,,H,,O, (m/z 364.1528, talc. 364.1523). UV$$’ 220nm. ‘HNMR (pyridine-d,): 61.32 (s, 3H, 18-H,), 1.36 (d, 3H, J=6.5 Hz, 17-H,), 1:56 (s, 3H, 20-H,), 1.90 (d, lH, J = 5.0 Hz, 5-H), 3.84 (dd, lH, J = 7.0, 10.0 Hz, 3-H), 4.08 (dd, lH, J =7.0,10.0 Hz, 16a-H),4.31 (dd, lH, J=4.0,10.0 Hz, 16b-H),4.39 (br s, lH, 7-H), 4.88 (d, lH, J=5.5Hz, 14-H), 5.13 (br d, lH, J=5.0Hz, 6-H) 6.16(s, lH, 11-H). Acknowledgement-BPY thanks Takasago Institute for Interdisciplinary Science for a fellowship.
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