Trimethylsilyldiazomethane
1021
and three further amounts of TMSCHN2 (0.5 mmol=0.25 mmol=0.25 mmol) were added dropwise
with intervals of 20 min. The ice-cooled mixture was stirred for further 30min, neutralized with
Et3N and concentrated. The residue was redissolved in Et2O and washed with cold H2O. After
drying (Na2SO4) and concentration to dryness the respective methyl ether was purified as described
below.
Ethyl {1R-(1ꢂ,4aꢃ,4bꢂ,8aꢃ,9ꢂ,10aꢂ)}-1,2,3,4,4a,4b,5,6,8a,9,10,10a-dodeca-
hydro-9-methoxy-1,4a-dimethyl-7-(1-methylethyl)-1-methoxycarbonyl-phenanthrene-9ꢃ-
yl-acetate (5a, C26H42O5)
The product was purified by CC using toluene:EtOAc¼ 3:1 as eluent. Yield 42%; colourless oil;
1
Rf ¼ 0.57 (silica, toluene:EtOAc¼ 3:1); H NMR (400MHz, CDCl3): ꢀ ¼ 0.81 (s, CH3-18), 0.95 (d,
J ¼ 6.8 Hz, CH3-16), 0.96 (d, J ¼ 6.8 Hz, CH3-17), 1.03 (t, J ¼ ꢄ13Hz, H-1ax), 1.03–1.14 (m, H-11ax),
1.16 (s, CH3-19), 1.23 (t, J ¼ 7.2 Hz, CH3-25), 1.37 (d, J ¼ ꢄ13Hz, H-6eq), 1.40 (t, J ¼ ꢄ11 Hz, H-9),
1.50–1.60 (m, H-2ax, H-2eq), 1.52 (d, J ¼ ꢄ12 Hz, H-3eq), 1.72 (d, J ¼ ꢄ13Hz, H-1eq), 1.73 (d,
J ¼ ꢄ13Hz, H-11eq), 1.73–1.83 (m, H-3ax), 1.85 (t, J ¼ ꢄ13Hz, H-6ax), 1.91–1.96 (m, H-12ax,
H-12eq), 2.05 (dd, J ¼ 13.0, 2.3Hz, H-5), 2.16 (sept, J ¼ 6.8 Hz, H-15), 2.22 (d br, J ¼ 10.6 Hz, H-8),
2.53 (d, J ¼ 13.9Hz, H-22), 2.69 (d, J ¼ 13.9Hz, H-220), 3.05 (s, CH3-26), 3.60 (s, CH3-21), 4.11 (qd,
J ¼ 7.2, 2.8 Hz, H-24, H-240), 5.39 (s, H-14) ppm; 13C NMR (100 MHz, CDCl3): ꢀ ¼ 13.5 (C-18), 14.2
ꢀ
ꢀ
(C-25), 16.7 (C-19), 18.0 (C-2), 21.3 (C-16 ), 21.7 (C-17 ), 22.1 (C-11), 26.3 (C-12), 29.7 (C-6), 35.0
(C-15), 36.0 (C-10), 36.9 (C-3), 37.3 (C-1), 40.5 (C-22), 42.2 (C-8), 43.0 (C-5), 47.1 (C-4, C-9), 48.7
(C-26), 51.7 (C-21), 60.3 (C-24), 76.8 (C-7), 118.6 (C-14), 143.6 (C-13), 171.5 (C-23), 179.2 (C-20)
 Ã
 Ã
26
26
ppm;
ꢂ
¼ ꢁ3.3ꢂ cm2 gꢁ1; (c ¼ 0.34, CH2Cl2);
ꢂ
¼ ꢁ6.5ꢂ cm2 gꢁ1; (c ¼ 0.34, CH2Cl2); IR
D
546
(KBr): ꢄꢀ¼ 3436 (s), 2950 (s), 2924 (w), 1728 (s), 1463 (m), 1177 (s) cmꢁ1; UV (CH2Cl2): ꢁmax
(lg") ¼ 234.0 (2.12) nm; ESI-MS: m=z (%) ¼ 457 (56) [M þ Na]þ, 403 (38) [Mꢁ CH3O]þ, 343 (100);
HR-MS: m=z (%) ¼ 452.3345 (100) [Mþ NH4]þ, calculated for C26H46NO5: 452.3376.
Isoborneol methyl ether (5b)
The product was purified by CC using CH:EtOAc ¼ 5:1 as eluent. Yield 51%; colourless oil; Rf ¼ 0.64
(silica, CH:EtOAc¼ 5:1); NMR-data are in accordance with those reported in Ref. [26].
Acknowledgement
Ms. E. Prettner is gratefully acknowledged for performing UV- and MS-analysis. Dr. S. Glasl, Institute
of Pharmacognosy, University of Vienna, is thanked for performing the high-resolution MS spectra.
We are also grateful to S. Kolleritsch and A. Karner for their engagement during their diploma thesis.
References
[1] Black TH (1983) Aldrichimica Acta 16: 3
[2] Hashimoto N, Aoyama T, Shioiri T (1981) Chem Pharm Bull 29: 1475
[3] For a review see: Shioiri T, Aoyama T (1993) Adv Use Synthons Org Chem 1: 51
[4] Lappert MF, Lorberth J (1967) Chem Commun 16: 836
[5] Shioiri T, Aoyama T, Mori S (1993) Org Synth Coll Vol 8: 612
[6] Shioiri T, Yamada S (1984) Org Synth 62: 187
[7] Corey EJ, Cantrall EW (1959) J Am Chem Soc 81: 1745
[8] Wirthlin T, Wehrli H, Jeger O (1974) Helv Chim Acta 57: 351
[9] Shimagaki M, Tahara A (1975) Tetrahedron Lett 21: 1715
[10] Geiwiz J, Haslinger E (1995) Helv Chim Acta 78: 818