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crude was purified by silica gel column chromatography (hexane/
AcOEt 6:4) to afford (3aR,9aR,10aR)-13 in 72% yield. White solid.
Mp 173–174 °C (diisopropyl ether). ½a D23
¼ ꢂ83:0 (c 0.91, CHCl3).
ꢁ
IR (nujol):
m .
= 1682 cmꢂ1 1H NMR (400 MHz, CDCl3) d: 1.26–1.37
(m, 1H), 1.41–1.50 (m, 2H), 1.74–1.81 (m, 1H), 1.83–2.00 (m,
3H), 2.14 (s, 3H), 2.33 (s, 3H), 2.34–2.37 (m, 1H), 2.38–2.42 (m,
1H), 2.52 (s, 3H), 3.60–3.68 (m, 1H), 4.16 (d, J = 10.2 Hz, 1H),
4.43–4.50 (m, 1H), 5.06–5.13 (m, 1H). 13C NMR (100 MHz, CDCl3)
d: 18.9 (q), 19.4 (q), 23.3 (t), 25.0 (t), 33.2 (t), 33.3 (t), 42.8 (t),
50.5 (d), 57.6 (d), 77.4 (d), 128.4 (s), 133.1, (s), 134.4 (s), 136.1
(s), 157.4 (s), 163.1 (s). MS: m/z 380 (M+). Anal. Calcd for
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C19H22Cl2N2O2: C, 59.85; H, 5.82; N, 7.35. Found: C, 59.99; H,
5. (a) Jeffery, T.; Galland, J.-C. Tetrahedron Lett. 1994, 35, 4103–4106; (b) Jeffery, T.
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1998, 39, 5751–5754.
5.76; N, 7.26.
Single crystals suitable for X-ray diffraction were obtained from
CHCl3. Relevant crystal data for 13: C19H22Cl2N2O2, FW =
6. (a) Broggini, G.; Molteni, G.; Zecchi, G. Synthesis 1995, 647–648; (b) Broggini,
G.; Zecchi, G. Gazz. Chim. Ital. 1996, 126, 479–488; (c) Broggini, G.; Folcio, F.;
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column, mobile phase: hexane/iPrOH = 4:1, flow rate 0.8 ml minꢂ1).
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381.3 g molꢂ1
,
yellow prism. k(Mo-K
orthorhombic Pbca, a = 10.068(6), b = 13.927(7), c = 26.076(7) Å,
V = 3656(3) Å3, Z = 8, F(000) = 1600, calc = 1.385 g cmꢂ3
(Mo-
) = 0.370 mmꢂ1. With 226 parameters, the R, wR figures of merit
reached final values of 0.057, 0.119 for the 1917 observed reflec-
tions [I >2 (I)], and of 0.115, 0.143 for the 3303 unique reflections.
a) = 0.71073 Å, T = 298 K;
q
, l
Ka
r
Goodness of fit, highest peak and deepest hole reached final values
of 1.026, 0.21 e Åꢂ3 and ꢂ0.21 e Åꢂ3. The crystallographic data
(excluding structure factors) for 13 have been deposited with the
Cambridge Crystallographic Data Centre as supplementary
publications number 802923. Copies of the data can be obtained,
free of charge, on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK, (fax: +44 (0)1223 336033 or e-mail: deposit@
ccdc.cam.ac.uk).
4.9.1. (3aS,9aS,10aS)-3-(3,5-Dichloro-2,4,6-trimethylphenyl)-
3a,6,7,8,9,9a,10,10a-octahydroisoxazolo[5,4-b]quinolizin-4-one
(3aS,9aS,10aS)-13
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Obtained in 68% yield from (S)-12 according to the procedure
described for the enantiomer. ½a D23
¼ þ87:2 (c 0.89, CHCl3). Anal.
ꢁ
Calcd for C19H22Cl2N2O2: C, 59.85; H, 5.82; N, 7.35. Found: C,
59.71; H, 5.93; N, 7.41
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Acknowledgments
We are grateful to MIUR for financial support and to the Centro
Interuniversitario di Ricerca sulle Reazioni Pericicliche e Sintesi di
Sistemi Etero e Carbociclici.
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