Stereocontrolled acid cyclization of (+)-hanphillin

Full text of DOI:10.1134/S107042801405025X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 5, pp. 757–758. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © N. Merkhatuly, S.B. Abeuova, A.N. Iskanderov, S.K. Aldabergenova, B.B. Togizbaeva, 2014, published in Zhurnal Organicheskoi
Khimii, 2014, Vol. 50, No. 5, pp. 767–768.
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Stereocontrolled Acid Cyclization of (+)-Hanphillin
N. Merkhatuly, S. B. Abeuova, A. N. Iskanderov,
S. K. Aldabergenova, and B. B. Togizbaeva
Buketov Karaganda State University, Universitetskaya ul. 28, Karaganda, 100028 Kazakhstan
e-mail: merhatuly@ya.ru
Received September 27, 2013
DOI: 10.1134/S107042801405025X
In extension of our research in the field of
biomimetic transformations of germacranic
sesquiterpene γ-lactones [1, 2] we performed by the
action of formic acid a stereocontrolled transannular
carbocyclization of Е,Е-germanocranolide hanphillin
(I) isolated from Noble Yarrow (Achillea nobilis L.),
and obtained new trans-fused 5α(Н),10β(СH3)-
eudesmanolides II and III in the yields of 65 and 30%
respectively.
and С6Н5СО3Н in СH2Сl2 at room temperature giving
trans-eudesmanolides formerly isolated from plant
sources [3, 4] epiartekalin (IV) and ridentin-В (V) in
45 and 53% yields (Scheme 2).
Compounds II and III. To a solution of 0.3 g
(1.2 mmol) of compound I in 15 mL of СНСl3 was
added dropwise at room temperature 4.6 mL of 99%
НСО2Н. The reaction mixture was stirred at room
temperature, then washed with 10% solution of
NaHCO3 (2 × 10 mL), with water (3 × 10 mL), dried
with MgSO4, the solvent was distilled off in a vacuum.
The residue (0.33 g) was chromatographed on a
column packed with silica gel (eluent hexane–ethyl
acetate, 2 : 3 and 1 : 4).
As shown in the scheme the acid-catalyzed 5,10-
carbocyclization of compound I proceeds evidently
through a regioselective protonation of the most
electron-donor and spatially available Δ1,10-double
bond of compound I followed by a stereospecific
nucleophilic attack by the Δ4,5-double bond leading via
a tertiary carbocation to the trans-fused eudesmano-
lides II and III (Scheme 1).
3-Oxoeudesm-11(13)-en-6,12-olide, or
(3aS,5aS,9R,9aS,9bS)-5a,9-dimethyl-3-methylidene-
octahydronaphtho[1,2-b]furan-2,8(3H,4H)-dione
(II). Yield 0.193 g (65%). Rf 0.54 (hexane–ethyl
acetate, 2 : 3). Colorless crystals, mp 136–138°С.
The stereocontrolled 5,10-carbocyclization of
compound I occurs also in the presence of СН3СО3Н
Scheme 1.
H+
1
10
5
H+
4
+
HO
HO
HO
H
O
O
O
O
O
O
_H+
I
H
H
H
O
H
O
HO
H
H
O
O
O
III
II
757

MERKHATULY et al.
758
(1Н, Н13, J 3.5 Hz), 5,92 d (1Н, H15, J 1 Hz), 6.26 d
Scheme 2.
(1Н, Н13, J 3.5 Hz). Mass spectrum, m/z (Irel, %): 248
(44.7) [М]+. Found, %: С 72.33; Н 7.81. С15Н20О3.
Calculated, %: С 72.58; Н 8.06.
OH
OH
H
O
H
H
O
H
IR spectra were recorded on a spectrophotometer
HO
O
1
H
H
Avatar-360 from pellets with KBr. Н NMR spectra
were registered on a spectrometer Bruker Avance-400
(operating frequency 400.13 МHz), solvent СDCl3,
internal reference TMS. Mass spectra were obtained on
an instrument Agilent 7890А. Specific rotation was
measured on a polarimeter Perkin-Elmer 141. Melting
points were determined on a small heating block
Boёtius. TLC was carried out on Silufol UV-254
plates.
O
O
IV
V
[α]D18 +96о (с 0.02, CHCl3). IR spectrum, ν, cm–1: 1760
1
(С=О), 1700 (С=О), 1640 (С=С). Н NMR spectrum,
δ, ppm: 1.43 s (3Н, СН3-С10), 1.68 br.s (3Н, СН3-С4),
4.12 q (1Н, Н6, J 10, 8.5 Hz), 5.52 d (1Н, Н13, J 3.5 Hz),
6.26 d (1Н, Н13, J 3.5 Hz). Mass spectrum, m/z (Irel,
%): 248 (32.4) [М]+. Found, %: С 72.38; Н 7.87.
С15Н20О3. Calculated, %: С 72.58; Н 8.06.
REFERENCES
3-Hydroxyeudesma-4(15),11(13)-dien-6,12-olide,
or (3aS,5aS,9aR,9bS)-8-hydroxy-5a-methyl-3,9-
dimethylidenedecahydronaphtho[1,2-b]furan-
2(3H)-one (III). Yield 0. 074 g (30%). Rf 0.37
(hexane–ethyl acetate, 1 : 4). Colorless crystals, mp
175–177°С. [α]D18 +106о (с 0.02, CHCl3). IR spectrum,
1. Merkhatuly, N., Zhokizhanova, S.K., Balmagambe-
tova, L.T., and Adekenov, S.M., Russ. J. Gen. Chem.,
2006, vol. 76, p. 1347.
2. Merkhatuly, N., Vestn. Karagand. Gos. Univer., Ser.
Khim., 2008, no 2, p. 46
3. Irwin, M.A. and Geissman, T.A., Phytochem., 1973,
vol. 12, p. 871.
4. Geissman, T.A., Griffin, T.S., and Irwin, M.A.,
Phytochem., 1969, vol. 8, p. 871.
1
ν, cm–1: 1760 (С=О), 1650, 1640 (С=С). Н NMR
spectrum, δ, ppm: 1.43 s (3Н, СН3С10), 4.12 q (1Н,
Н6, J 10, 8.5 Hz), 5,26 d (1Н, H15, J 1 Hz), 5.52 d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 5 2014