A. Dommisse, J. Wirtz, K. Koch, W. Barthlott, T. Kolter
FULL PAPER
methylaminopyridine (36.8 mg, 300 µmol). The mixture was cooled
to 0 °C and dicyclohexylcarbodiimide (1.24 g, 6 mmol) was added
in portions, and the mixture was stirred for two hours at 0 °C and
for 3 d at room temp. The reaction mixture was evaporated, and
the remaining residue was purified by silica gel column chromatog-
raphy (cyclohexane/ethyl acetate, 80:1). The two products were iso-
lated as colourless oils in a combined yield of 960 mg (92.0%). The
chromatographic separation afforded pure (R,R)-5 [24% of total
product, Rf = 0.57 (cyclohexane/ethyl acetate, 10:1)], (R,S)-5 [19%
of total product, Rf = 0.52 (cyclohexane/ethyl acetate, 10:1)] and a
mixture of both compounds (57%) that could be further resolved
by repeated chromatography. (R,R)-5: [α]2D0 = –27.6 (c = 0.185,
CHCl3); (R,S)-5: [α]2D0 = –51.0 (c = 0.059, CHCl3).
and 3. As demonstrated for the intermediates (R,S)-5 and
(R,R)-5, the compounds are obtained in high enantiomeric
purity. The title compounds are currently used to investi-
gate the influence of the stereochemistry on tubular wax
formation in vitro.
Experimental Section
General: Glassware was flame-dried and reactions were carried out
under an argon atmosphere. Chemical reagents were purchased
from Fluka (Buchs, Switzerland) and Sigma (Taufkirchen, Ger-
many). Column chromatography was performed with silica gel 60
(Merck, Darmstadt, Germany). 1H NMR spectra were recorded
with Bruker AM-400 (400 MHz) and Bruker AM-300 (300 MHz)
(2R)-(S)-Tridec-1-en-4-yl 2-Methoxy-2-phenylacetate [(R,S)-5]: 1H
NMR (400 MHz, CDCl3, 25 °C): δ = 7.43 (m, 2 H), 7.33 (m, 3 H),
3
3
3
5.71 (ddt, JH,H = 17.1 Hz, JH,H = 10.1 Hz, JH,H = 7.0 Hz, 1 H),
instruments with the solvent as an internal standard (CDCl3, δH
=
3
4
2
5.04 (dtd, JH,H = 17.1 Hz, JH,H = 3.4 Hz, JH,H = 1.2 Hz, 1 H),
7.24 ppm). 13C NMR spectra were recorded with Bruker AM-400
(100 MHz) and Bruker AM-300 (75 MHz) instruments with the
solvent as an internal standard (CDCl3, δC = 77.0 ppm). 13C NMR
spectra were recorded in broadband decoupled mode and multi-
plicities were determined by using a DEPT pulse sequence. ESI-
TOF-mass spectra were recorded in positive ion mode with a Q-
TOF 2 mass spectrometer (Micromass, Manchester, UK) equipped
with a nanospray source. Analytes were dissolved in chloroform/
methanol and were injected into the mass spectrometer by glass
capillaries by using a capillary voltage of 1000 V and a cone voltage
of 50 V. Instrument calibration was done with a mixture of sodium
iodide and cesium iodide dissolved in 50% aqueous 1-propanol.
EI-mass spectra were recorded in positive ion mode with a MAT
95 mass spectrometer (Finnigan, Manchester, UK) in the analytical
department of the Kekulé-Institut für Organische Chemie und Bio-
chemie, Bonn.
3
4
2
5.01 (dtd, JH,H = 10.1 Hz, JH,H = 2.0 Hz, JH,H = 1.2 Hz, 1 H),
3
4.95 (pseudo quintet, JH,H = 6.3 Hz, 1 H), 4.71 (s, 1 H), 3.41 (s, 3
H), 2.23 (m, 2 H), 1.42 (m, 2 H), 1.21 (m, 14 H), 0.88 (t, JH,H
3
=
7.1 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3, 25 °C): δ = 170.7,
136.8, 133.8, 128.7, 127.5, 126.3, 118.0, 83.0, 74.5, 57.6, 39.0, 33.7,
32.1, 30.4, 29.7, 29.6, 29.5, 27.2, 25.0, 22.9, 14.4 ppm. MS (FAB):
m/z (%) = 347.2 (16) [M + H]+.
(2R)-(R)-Tridec-1-en-4-yl 2-Methoxy-2-phenylacetate [(R,R)-5]: 1H
NMR (400 MHz, CDCl3, 25 °C): δ = 7.43 (m, 2 H), 7.33 (m, 3 H),
3
3
3
5.45 (ddt, JH,H = 16.7 Hz, JH,H = 10.6 Hz, JH,H = 7.1 Hz, 1 H),
3
4
2
4.89 (m, 1 H), 4.75 (dtd, JH,H = 10.6 Hz, JH,H = 2.1 Hz, JH,H
1.1 Hz, 1 H), 4.74 (dtd, JH,H = 16.7 Hz, JH,H = 3.4 Hz, JH,H
=
=
3
4
2
1.1 Hz, 1 H), 4.69 (s, 1 H), 3.41 (s, 3 H), 2.11 (m, 2 H), 1.43 (m, 2
3
H), 1.23 (m, 14 H), 0.88 (t, JH,H = 7.1 Hz, 3 H) ppm. 13C NMR
(100 MHz, CDCl3, 25 °C): δ = 170.8, 136.8, 133.4, 128.9, 128.8,
127.5, 118.0, 83.1, 74.7, 57.7, 38.7, 33.9, 32.2, 30.5, 29.8, 29.7, 29.6,
29.5, 27.2, 25.5, 23.0, 14.4 ppm. MS (FAB): m/z (%) = 347.2 (16)
[M + H]+.
Tridec-1-en-4-ol (3): Commercially available decanal (1) was dis-
tilled (4.8 mbar, 80 °C) prior to use and kept under an argon atmo-
sphere. Decanal (1; 15.7 mL, 82.2 mmol) was dissolved in diethyl
ether (85 mL) and the solution was cooled to –42 °C; a solution of
allylmagnesium bromide in diethyl ether (2; 1.0 , 100 mL,
100 mmol, 1.2 equiv.) was added drop wise. After one hour, the
reaction mixture was brought to room temp. and stirred for one
additional hour. A saturated aqueous ammonium chloride solution
(85 mL) was added, and the aqueous phase was separated and ex-
tracted three times with diethyl ether. The collected organic phases
were washed with an aqueous NaHCO3 solution and then with
water. The organic phase was dried with sodium sulfate, and the
solvent was removed under reduced pressure. Purification by col-
umn chromatography on silica gel (cyclohexane/ethyl acetate, 10:1)
yielded 3 (16.07 g, 81.0 mmol, 99%, Rf = 0.51) as a colourless li-
Nonacos-12-en-10-yl 2-Methoxy-2-phenylacetate [(R,S)-7]: (R,S)-5
(12.0 mg, 34.6 µmol) was dissolved in dichloromethane (5 mL) and
octadec-1-en (22.5 µL, 70.1 µmol, 2 equiv.) and Grubbs 2nd gener-
ation catalyst (6; 5.3 mg, 17 mol-%) were added. The solution was
then heated at reflux for 4 h, during which the solution colour
turned from red into brown. Purification by silica gel column
chromatography (cyclohexane/ethyl acetate, 40:1) gave product
(R,S)-7 (11.4 mg, 20.0 µmol, 58%, Rf = 0.26) as a colourless oil.
(R,R)-7: Yield: 87% (50.2 mg, 87.9 µmol, Rf = 0.27) from (R,R)-5
(35.1 mg).
(R,S)-7: 1H NMR (400 MHz, CDCl3, 25 °C): δ = 7.44 (m, 2 H),
7.34 (m, 3 H), 5.37 (dt, 3JH,H = 15.3 Hz, 3JH,H = 6.5 Hz, 1 H), 5.29
(dt, 3JH,H = 15.3 Hz, 3JH,H = 6.7 Hz, 1 H), 4.90 (tt, 3JH,H = 6.2 Hz,
3JH,H = 6.2 Hz, 1 H), 4.73 (s, 1 H), 3.41 (s, 3 H), 2.23 (m, 1 H),
1.94 (m, 1 H), 1.69 (m, 2 H), 1.43 (m, 2 H), 1.25 (m, 42 H), 0.88
(t, 3JH,H = 7.1 Hz, 6 H) ppm. 13C NMR (100 MHz, CDCl3, 25 °C):
δ = 170.7, 136.9, 134.3, 128.8, 128.7, 127.5, 127.4, 124.8, 83.0, 75.1,
57.6, 37.7, 33.6, 32.8, 32.2, 32.1, 30.4, 30.0, 29.9, 29.8, 29.7, 29.6,
29.5, 29.4, 27.6, 25.1, 22.9, 14.4 ppm. MS (ESI): m/z (%) = 593.40
(38) [M + Na]+, 1163.80 (100) [2M + Na]+.
3
quid. 1H NMR (400 MHz, CDCl3, 25 °C): δ = 5.83 (dddd, JH,H
3
3
3
= 17.6 Hz, JH,H = 10.0 Hz, JH,H = 7.9 Hz, JH,H = 6.6 Hz, 1 H),
3
2
4
5.13 (ddt, JH,H = 17.6 Hz, JH,H = 2.0 Hz, JH,H = 1.2 Hz, 1 H),
3
2
4
5.12 (ddt, JH,H = 10.0 Hz, JH,H = 2.0 Hz, JH,H = 1.2 Hz, 1 H),
3
3
3
3.62 (ddt, JH,H = 7.9 Hz, JH,H = 7.9 Hz, JH,H = 4.2 Hz, 1 H),
2.29 (dddd, 3JH,H = 13.9 Hz, 3JH,H = 6.6 Hz, 3JH,H = 4.2 Hz, 4JH,H
= 1.2 Hz, 1 H), 2.13 (dddd, 3JH,H = 13.9 Hz, JH,H = 7.9 Hz, 3JH,H
3
4
= 7.9 Hz, JH,H = 1.2 Hz, 1 H), 1.63 (m, 1 H), 1.45 (m, 2 H), 1.26
(m, 14 H), 0.85 (t, 3JH,H = 7.0 Hz, 3 H) ppm. 13C NMR (100 MHz,
CDCl3, 25 °C): δ = 135.3, 118.3, 71.0, 42.3, 37.2, 32.2, 31.9, 30.0,
29.9, 29.7, 26.0, 23.0, 14.4 ppm. MS (ESI): m/z (%) = 221.12 (9)
[M + Na]+.
(R,R)-7: 1H NMR (400 MHz, CDCl3, 25 °C): δ = 7.36 (m, 2 H),
7.27 (m, 3 H), 5.18 (dt, 3JH,H = 15.2 Hz, 3JH,H = 1.3 Hz, 1 H), 4.95
3
3
(tt, JH,H = 15.2 Hz, JH,H = 1.4 Hz, 1 H), 4.83 (m, 1 H), 4.67 (s,
1 H), 3.34 (s, 3 H), 2.34 (m, 1 H), 2.03 (m, 1 H), 1.76 (m, 2 H),
3
Tridec-1-en-4-yl 2-Methoxy-2-phenylacetate (5): To a solution of 3
(597 mg, 3.01 mmol) in dichloromethane (15 mL), was added (R)-
α-methoxyphenylacetic acid (4, 1 g, 6.02 mmol, 2 equiv.) and di-
1.44 (m, 2 H), 1.19 (m, 42 H), 0.87 (t, JH,H = 7.1 Hz, 3 H), 0.85
(t, 3JH,H = 7.1 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3, 25 °C):
δ = 169.7, 135.9, 133.3, 127.9, 127.8, 126.5, 123.6, 82.1, 74.4, 56.6,
3510
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Eur. J. Org. Chem. 2007, 3508–3511