D. Sanhes et al. / Tetrahedron Letters 49 (2008) 6720–6723
6723
14. For a recent related paper see: Burgess, K. L.; Corbett, M. S.; Eugenio, P.;
Lajkiewicz, N. J.; Liu, X.; Sanyal, A.; Yan, W.; Yuan, Q.; Snyder, J. K. Bioorg. Med.
Chem. 2005, 13, 5299–5309.
15. Procedures and characterization data for compounds 1–4:
Synthesis of the compound 1: A solution of anthracene (5.00 g, 28.1 mmol) and
maleic anhydride (3.30 g, 33.7 mmol) in toluene (100 mL) was refluxed for
72 h. The reaction mixture was then cooled, filtered and the solid obtained
washed with diethylether and dried under reduced pressure. Crystallisation
from ethyl acetate gave a white powder (6.94 g, 89%).
methodology could open a useful access to prepare 1,2,3,4-tetrahy-
droanthracenes by retro Diels–Alder reaction from the correspond-
ing dicarboximides.14,15
The isomeric purity of 2 should be related to the high barrier
associated to the rotation around the N–CH bond. For 3, this fact
is even more evident due to the more sterically demanding cyclo-
hexyl group in comparison with the phenyl group for 2. In addition,
Synthesis of the compound 2: A solution of 1 (2.00 g, 7.3 mmol) and (S)-a-
a strong CH/p interaction between a methylene group of the cyclo-
methylbenzylamine (1.85 mL, 14.5 mmol) in toluene (90 mL) was refluxed for
72 h in presence of molecular sieves 4 Å. The reaction mixture was then cooled,
filtered, and the solvent removed under reduced pressure. The yellow residue
obtained was dissolved in dichloromethane (20 mL) and washed with
ammonium chloride saturated aqueous solution (3 Â 20 mL). The combined
organic layers were dried on anhydrous Na2SO4, filtered, and the solvent
evaporated under vacuum leading to a white powder. After purification by
column chromatography on silica gel with dichloromethane, 2 was obtained as
a white powder (1.96 g, 71%). Melting point: 163 °C. 1H NMR (400 MHz, DMSO-
d6: d 7.40 (m, 2H, Harom), 7.30 (m, 1H, Harom), 7.20 (m, 1H, Harom), 7.16 (m, 7H,
Harom), 6.70 (m, 2H, H4 and H8), 4.87 (q, 3J = 7.2 Hz, 1H, H1), 4.79 (d, 3J = 2.8 Hz,
1H, H13), 4.77 (d, 3J = 3.0 Hz, 1H, H20), 3.28 (dd, 3J = 8.6 Hz, 3J = 3.0 Hz, 1H,
hexyl fragment with the aromatic moiety of the backbone avoids
the formation of the corresponding anti-isomer. Consequently,
for less sterically demanding groups the rotation is favoured as
observed for 4.15
Acknowledgements
The authors thank Marc Vedrenne, Christian Pradel and Heinz
Gornitzka for their helpful collaboration in NMR, TEM and X-ray
diffraction analysis, respectively, and also the Centre National de
la Recherche Scientifique (CNRS) and the Université Paul Sabatier
for the financial support.
H11), 3.25 (dd, 3J = 8.6 Hz, 3J = 3.0 Hz, 1H, H12), 1.16 (d, 3J = 7.2 Hz, 3H, H2); 13
C
NMR (100.6 MHz, DMSO-d6: d 176.7 (C9), 176.6 (C10), 142.6, 139.9, 139.8,
139.7, 128.5, 127.1, 127.0, 126.9, 126.7, 126.5, 125.2, 124.6, 124.5, 49.2, 46.6,
46.5, 45.2, 16.6 (C2). Mass spectrometry (ES, m/z): 379. Anal. Calcd for
C26H21NO2 (M = 379.45): C, 82.30; H, 5.58, N, 3.69. Found: C, 82.17; H, 5.29, N,
3.66. Single crystals were obtained from diethylether solution of 2.
Supplementary data
Synthesis of compound 3:
A solution of 2 (30 mg, 0.08 mmol) and
[Ru(COD)(COT)] (28 mg, 0.08 mmol) in dry tetrahydrofuran (10 mL) was
exposed under 3 bar H2 pressure during 4 h at room temperature. The
solvent was then removed under vacuum and the residue obtained was
dissolved in diethylether (10 mL) and washed with water (3 Â 10 mL). The
combined organic layers were dried on anhydrous Na2SO4 and the solvent
evaporated under vacuum, leading to a white powder. Crystallisation from
dichloromethane/pentane (1:1 v/v) gave colourless crystals suitable for single-
crystal X-ray diffraction (32 mg, 99%). 1H NMR (500 MHz, THF-d8: d 7.16 (m,
2H, Harom, H23 and H26), 7.07 (m, 2H, Harom, H24 and H25); 3.40 (m, 1H, H1);
3.22 (s, 2H, H13 and H20), 3.09 (m, 2H, H11 and H12), 2.11 (m, 2H, H14 and
H19), 1.64 (m, 2H, H3, H4), 0.64 (m, 1H, H4), 0.35 and 0.25 (m, 2H, H8), 1.35
and 0.64 (m, 4H, H15 and H18), 1.52 and 1.44 (m, 4H, H16 and H17), 1.52 and
1.00, 1.42 and 0.88, 1.64 and 1.14 (m, 6H, H5, H6 and H7), 0.83 (d, 6.5 Hz, 3H2);
13C NMR (125 MHz, THF-d8: d 177.27 (C9 or C10), 177.17 (C9 or C10), 137.51
(C21 or C22), 137.45 (C21 or C22), 126.78, 126.60, 126.56, 126.53 (C23, C24,
C25, C26), 51.96 (C1), 44.49 (C13 or C20), 44.43 (C13 or C20), 42.22 (C11 and
C12), 38.45 (C3), 37.69 (C14 or C19), 37.68 (C14 or C19), 30.17 (C4), 28.80 (C8),
26.09 (C5 or C6 or C7), 25.92 (C5 or C6 or C7), 25.78 (C5 or C6 or C7), 23.70 (C15
or C18), 23.69 (C15 or C18), 19.24 (C16 and C17), 14.29 (C2). HRMS (ES+): m/z
(100%) calcd for C26H33NO2 391.5522, found 392.2605.
Synthesis of the compound 4: A solution of 1 (1.00 g, 3.6 mmol) and (1S,3S)-2-
amino-1-phenyl-1,3-propandiol (1.21 g, 7.2 mmol) in toluene (120 mL) was
refluxed for 12 h in the presence of molecular sieves 4 Å. The reaction mixture
was monitored by TLC (hexane/ethyl acetate = 3/2), then cooled, filtered, and
the solvent removed under reduced pressure. The residue obtained was
dissolved in dichloromethane (20 mL) and washed with ammonium chloride
saturated aqueous solution (3 Â 20 mL). The combined organic layers were
dried on anhydrous Na2SO4, filtered and the solvent evaporated under vacuum
leading to a white powder recrystallised from in ethyl acetate (1.34 g, 87%).
Melting point: 200 °C. 1H NMR (300 MHz, CDCl3: d 7.39–7.15 (m, 13H), 5.03 (d,
3J = 7 Hz, 1H), 4.78 (m, 2H), 4.10 (q, 3J = 7 Hz, 1H), 3.15 (m, 4H). 13C NMR
(75.5 MHz, CDCl3): 179.9 (C), 176.4 (C), 141.1 (C), 141.0 (C), 139.0 (C), 138.9
(C), 129.1 (CH), 128.5 (CH), 128.2 (CH), 127.9 (CH), 127.2 (CH), 127.1 (CH),
126.9 (CH), 126.8 (CH), 125.7 (CH), 125.3 (CH), 125.2 (CH), 125.1 (CH), 124.3
(CH), 70.7 (CH), 59.8 (CH2), 59.6 (CH), 46.8 (CH), 46.1 (CH), 45.5 (CH), 45.4 (CH).
Mass spectrometry (ESI, m/z): 448.4 [M+Na], 426.4 [M+H]. Anal. Calcd for
C27H23NO4 (M = 425.48): C, 76.22, H, 5.45, N, 3.29. Found: C, 76.20, H, 5.24, N,
3.32.
Supplementary data associated with this article can be found, in
References and notes
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CCDC 690719 for
2 and CCDC 690720 for 3 contain the supplementary
crystallographic data for this Letter. These data can be obtained free of charge
Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax:
(internat.) +44-1223/336-033; e-mail: deposit@ccdc.cam.ac.uk].