Oxidation of terpenoids with a cyclohexanone fragment by performic acid

Full text of DOI:10.1007/s10600-014-1082-x

Chemistry of Natural Compounds, Vol. 50, No. 4, September, 2014 [Russian original No. 4, July–August, 2014]
OXIDATION OF TERPENOIDS WITH A CYCLOHEXANONE
FRAGMENT BY PERFORMIC ACID
V. A. Vydrina, Yu. A. Galkina, R. R. Muslukhov,
*
A. A. Kravchenko, and G. Yu. Ishmuratov
Performic acid is a reactive, inexpensive, and available reagent for Baeyer–Villager oxidation of ketones that is used
infrequently in the chemistry of cyclic terpene ketones, e.g., only for the oxidation of isocaranone [1] and allobetulone [2].
The goal of the present work was to expand the scope of this reagent for the oxidation of terpenoids with a cyclohexanone
fragment. We found that Baeyer–Villager oxidation of 28-oxoallobetulin-3-one (1), carvomenthone (2), and menthone (3) by
performic acid occurred regio- and stereospecifically to give lactones 5–7, respectively. Oxidation of isomenthone (4) by
H O –HCOOH caused racemization of the asymmetric center with the isopropyl substituent (probably due to keto–enol
2
2
tautomerism under acidic conditions) to give a mixture of diastereomeric lactones 7 and 8 (1:1), in contrast with diastereospecific
m-chloroperbenzoic acid [3].
O
O
O
O
a
O
a
O
O
98%
O
O
88%
O
O
O
1
5
2
6
a
a
O
7
+
98%
95%
O
O
O
7
4
8
3
a. HCOOH, H O (30%), CH Cl
2
2
2
2
We used equipment of the CCU Khimiya, IOC, USC, RAS. IR spectra were recorded from thin layers on an
IR-Prestige-21 instrument (Fourier Transform Spectrophotometer, Shimadzu). NMR spectra were recorded in CDCl with
3
TMS internal standard on high-resolution AM-300 and Avance III 500 MHz spectrometers (Bruker, operating frequency
1
13
13
300 MHz for H and 75.47 MHz for C). C NMR spectra were recorded using broad-band proton decoupling and in JMOD
mode. NMR resonances were assigned and SSCCs were determined using two-dimensional correlation spectroscopy COSY
(C–H) and COSY (H–H) and double resonance. NMR spectra were analyzed using literature data [4–7]. Chromatography
was carried out on Chrom-5 [column length 1.2 m, stationary phase silicone SE-30 (5%) on Chromaton N-AW-DMCS
(0.16–0.20 mm), operating temperature 50–300°C] and Chrom-41 [column length 2.4 m, stationary phase PEG-6000 (5%) on
Inerton AW-DMCS (0.125–0.160 mm), operating temperature 50–200°C] instruments with He carrier gas. Column
chromatography was performed on silica gel (Lancaster, 60–200 ꢀm). TLC used Sorbfil UV-254 plates (Krasnodar), hexane–
Et O eluent, and H SO –anisaldehyde detector. Optical rotation was measured on a PerkinElmer 241-MC polarimeter. Elemental
2
2
4
analyses of all compounds agreed with those calculated.
Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, 450054, Ufa, Prosp. Oktyabrya,
71, fax: +7 (347) 235 60 66, e-mail: insect@anrb.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 4, July–August,
2014, pp. 665–666. Original article submitted April 1, 2014.
©
774
0009-3130/14/5004-0774 2014 Springer Science+Business Media New York

Oxidation of Terpene Ketones (1–4). A mixture of freshly distilled HCOOH (5.0 mL) and H O (1.6 mL, 30%) was
2
2
stirred at 10°C, treated dropwise with the appropriate ketone (1–4, 10.0 mmol) in CH Cl (10 mL), stirred at room temperature,
2
2
and treated dropwise at 3-h intervals with two portions (1.6 ml each) of H O (30%). After 4 h, the mixture was poured into
2
2
cold H O (10 mL) and extracted with CH Cl (3 ꢁ 50 mL). The extract was washed successively with distilled H O and
2
2
2
2
saturated NaHCO and NaCl solutions, dried over MgSO , and evaporated.
3
4
19ꢂ,28-Epoxy-28-oxo-4-hydroxy-3,4-seco-18ꢃ-oleanan-3-oic Acid Lactone (5). Compound 1 (4.5 g), which is
21
available from betulin [8], afforded the dilactone 5 (4.05 g, 88%), R 0.46 (PE–MTBE, 1:1), [ꢃ] +107.3° (c 1.07, CHCl ).
f
D
3
–1
1
IR spectrum (KBr, ꢄ, cm ): 1757 [C(O)O– in ring A], 1763 [C(O)O– in ring E]. H NMR spectrum (CDCl , ꢅ, ppm, J/Hz):
3
0.69 (3Í, s, C-27), 0.87 (3H, s, H-25), 0.87 (3H, s, H-30), 0.88 (3H, s, H-23), 1.03 (3H, s, H-29), 1.08 (3H, s, H-24), 1.09 (3H,
s, H-26), 1.15–1.21 (1H, m, H -11), 1.26–1.33 (1H, m, H-13), 1.29–1.30 (1H, m, H -12), 1.30–1.36 (1H, m, H -16), 1.30–1.41
a
e
a
(1H, m, H -12), 1.41 (1H, dd, J = 10.0, 2.3, H-9), 1.43–1.53 (2H, m, H-21), 1.25–1.40, 1.37–1.42, 1.52–1.60 (each 2Í, m,
e
Í-6, 7, 15), 1.52–1.67 (2H, m, H-22), 1.53 (1H, dd, J = 12.8, 2.3, H -11), 1.52 (1H, ddd, J = 13.3, 13.7, 5.6, H -1), 1.68 (1H,
e
a
dd, J = 9.5, 3.2, H -16), 1.76 (1H, d, J = 12.6, 1.9, H-5), 1.81 (1H, dd, J = 9.7, 3.2, H-18), 1.83 (1Í, ddd, J = 13.3, 4.8, 3.4,
e
13
Í -1), 1.93 (1H, s, H-19), 2.48 (1H, ddd, J = 14.4, 5.6, 3.4, H -2), 2.63 (1H, ddd, J = 14.4, 13.7, 4.8, H -2). C NMR spectrum
e
å
à
(CDCl , ꢅ, ppm): 13.44 (q, CÍ Ñ-27), 15.12 (q, Ñ-25), 18.74 (q, Ñ-26), 22.10 (t, Ñ-6), 23.42 (t, Ñ-11), 23.94 (q, Ñ-23), 25.46
3
3
(t, Ñ-15), 26.62 (t, Ñ-16), 26.82 (q, Ñ-30), 27.82 (t, Ñ-12), 28.73 (q, Ñ-24), 30.89 (q, Ñ-29), 31.89 (t, Ñ-21), 32.29 (t, Ñ-22),
32.34 (t, Ñ-7), 32.49 (t, Ñ-2), 33.56 (s, Ñ-20), 36.26 (d, Ñ-13), 39.47 (s, Ñ-14), 39.97 (s, Ñ-10), 39.97 (t, Ñ-1), 40.22 (s, Ñ-8),
46.11 (s, Ñ-17), 46.55 (d, Ñ-18), 51.86 (d, Ñ-9), 52.83 (d, Ñ-5), 85.99 (d, Ñ-19), 89.85 (s, Ñ-4), 175.20 (s, Ñ-3), 179.82 (s,
Ñ-28).
4R-Isopropyl-7-methyloxepan-2-one (6). Carvomenthone (2, 1.55 g) afforded carvomentholactone (6, 1.66 g, 98%).
13
The PMR and C NMR spectra were identical to those published [9, 10].
7S-Isopropyl-4R-methyloxepan-2-one (7). (–)-Menthone (3, 1.55 g) afforded (–)-mentholactone (7, 1.66 g, 98%),
20
13
[ꢃ] –26.5° (c 1.9, CHCl ). The PMR and C NMR spectra were identical to those published [11].
D
3
7R-Isopropyl-4R-methyloxepan-2-one (8). (–)-Isomenthone (4, 1.55 g) afforded a mixture (1.60 g, 98%) of
13
(–)-mentholactone (7) and isomentholactone (8) (1:1). The PMR and C NMR spectra were identical to those published [3].
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