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DOI: 10.1055/s-2002-32970
First Total Synthesis of (-)-1(10),5-Germacradien-4-ol
Publikationsverlauf
Publikationsdatum:
25. Juli 2002 (online)
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Abstract
This paper presents a total synthesis of (-)-1(10),5-germacradien-4-ol, a constituent of the needles of Scots pine and of the defence secretion from the larvae of the pine sawfly. The synthesis uses a strategy based on an intramolecular alkylation to form an unsaturated monocyclic 10-membered ring.
Key words
germacrane terpenoids - intramolecular alkylation - stereoselective synthesis
- 1
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4a Two
numbering systems of 1 occur in the literature.
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4b
Another system of numbering 1 is used e.g. in refs. 3,6,8,9,10,21,23.
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References
PHERODIP, Pine sawfly pheromones for sustainable management of European forests; European Community contacts, no. FAIR1-CT95-0339. Final report.
15Isolated yield of homogeneous substances. All new compounds showed satisfactory spectroscopic data based on data from 1H and 13C NMR, IR and MS.
17Attempted removal of the benzyl group with H2/Pd-C in MeOH was inefficient, whereas migration of the silyl group was observed in THF.
22Data of 2:
IR (neat, KBr): 2960, 2930, 2870, 1690, 1650, 1625, 1385, 1370,
1155, 1105, 990 cm-1; 1H
NMR* (250.13 MHz, CDCl3): δ 6.08 (dd, J = 16, 10 Hz, 1 H), 6.06 (d, J = 16 Hz, 1 H), 5.00-5.08
(m, 1 H), 2.65 (m, 1 H), 2.05-2.50 (m, 6 H), 1.91 (m, 1
H), 1.50-1.76 (m, 2 H), 1.49 (s, br, 3 H), 0.90 (d, J = 6.8 Hz, 3 H), 0.84 (d, J = 6.8 Hz, 3 H); significant shifts
of minor stable conformer, or 5Z-isomer: δ 6.64
(dd,
J = 16, 10 Hz,
1 H), 5.98 (d, br, J = 16 Hz,
1 H), 5.30 (m,
1 H), 1.30 (s, br, 3 H), 0.95 (d, J = 6.7 Hz, 3 H), 0.88 (d, J = 6.6 Hz, 3 H); 13C
NMR (62.9 MHz, CDCl3): δ 202.4, 149.7, 136.8,
135.4, 129.0, 52.8, 40.9, 40.4, 32.3, 28.0, 25.4, 20.8, 19.5, 15.6;
minor stable conformer, or 5Z-isomer: δ 201.7, 159.9,
141.1, 128.4, 126.6, 49.9, 38.9, 35.6, 34.4, 30.9, 25.4, 20.8, 20.7,
18.9; MS (EI, ion trap) m/z (rel.
int.): 206 (M+, 40), 189(15), 163(35), 136(100),
121(35), 107(40), 93(80), 79(70), 67(45); MS (CI, ion trap, CH3CN
as ionisation gas) m/z (rel.
int.): 207 (M + H+, 75), 189(100).
*Due
to the fact that this is a mixture of two stable conformers, or
5E/5Z isomers,
the 1H NMR characterisation is still pending.