1H), 3.11 (dd, J 7.5, 4 Hz, 2H), 2.90–2.83 (m, 1H), 2.45 (dt, J 16,
4 Hz, 1H); 13C NMR (CDCl3, 100 MHz) d = 147.6, 147.1, 131.7,
129.1, 127.4, 126.4, 111.7, 108.7, 65.9, 57.5, 55.9, 55.8, 46.0, 23.7;
HRMS (ES) Found: MH+ (ES), 232.1329. C14H18NO2 requires
MH+, 232.1338; LRMS m/z (ES) 232 (95%, MH+).
2 (a) L. M. Harwood and R. J. Vickers, in ‘Synthetic Applications of
1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural
Products’, eds. A. Padwa, and W. H. Pearson, Wiley, New Jersey, 2003,
ch. 3, p. 169; (b) C. Najera and J. M. Sansano, Curr. Org. Chem., 2003,
7, 1105; (c) I. Coldham and R. Hufton, Chem. Rev., 2005, 105, 2765;
(d) L. M. Stanley and M. P. Sibi, Chem. Rev., 2008, 108, 2887.
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Huisgen, W. Scheer and H. Ma¨der, Angew. Chem., Int. Ed. Engl., 1969,
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Commun., 1978, 109; (b) R. Grigg and J. Kemp, Tetrahedron Lett., 1980,
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Tetrahedron, 1988, 44, 4953.
Crispine A. The alkene 39 (100 mg, 0.43 mmol) was dissolved
in MeOH (3 mL) and stirred with Pd/C (~100 mg, 10 wt%)
under an atmosphere of hydrogen at room temperature. After
2 h, the mixture was filtered, evaporated and purified by column
chromatography on neutral alumina, eluting with MeOH–CH2Cl2
(5 : 95), to give crispine A (80 mg, 80%) as needles; mp 79–81 ◦C
5 (a) W. H. Pearson, P. Stoy and Y. Mi, J. Org. Chem., 2004, 69, 1919;
(b) W. H. Pearson, J. E. Kropf, A. L. Choy, I. Y. Lee and J. W. Kampf,
J. Org. Chem., 2007, 72, 4135.
◦
◦
(lit. gives the following: lit.10 87–89 C, lit.11a,b 88–89 C, lit.11g
76–78 ◦C, lit.11i 77–79 ◦C, other references do not mention m.p.);
Rf 0.18 [MeOH–CH2Cl2 (5 : 95)]; H NMR (CDCl3, 400 MHz)
6 (a) I. Coldham, K. M. Crapnell, J. D. Moseley and R. Rabot, J. Chem.
Soc., Perkin Trans. 1, 2001, 1758; (b) I. Coldham, K. M. Crapnell, J.-
C. Ferna`ndez, J. D. Moseley and R. Rabot, J. Org. Chem., 2002, 67,
6181; (c) I. Coldham, S. M. Pih and R. Rabot, Synlett, 2005, 1743; (d) I.
Coldham, B. C. Dobson, A. I. Franklin and S. R. Fletcher, Tetrahedron
Lett., 2007, 48, 873; (e) I. Coldham, A. J. M. Burrell, L. E. White, H.
Adams and N. Oram, Angew. Chem., Int. Ed., 2007, 46, 6159; (f) I.
Coldham, B. C. Dobson, S. R. Fletcher and A. I. Franklin, Eur. J. Org.
Chem., 2007, 2676; (g) A. J. M. Burrell, I. Coldham, L. Watson, N.
Oram, C. D. Pilgram and N. G. Martin, J. Org. Chem., 2009, DOI:
10.1021/jo8019913.
1
d = 6.59 (s, 1H), 6.55 (s, 1H), 3.83 (s, 3H), 3.82 (s, 3H), 3.39 (t, J
8.5 Hz, 1H), 3.19–3.14 (m, 1H), 3.09–2.97 (m, 2H), 2.74–2.50 (m,
3H), 2.34–2.27 (m, 1H), 1.98–1.79 (m, 2H), 1.75–1.65 (m, 1H); 13
C
NMR (CDCl3, 100 MHz) d = 147.2, 147.1, 130.9, 126.2, 111.2,
108.7, 62.9, 55.9, 55.8, 53.1, 48.3, 30.4, 28.0, 22.1; HRMS (ES)
Found: MH+ (ES), 234.1484. C14H20NO2 requires MH+, 234.1494;
spectroscopic data consistent with the literature.11
7 I. Coldham, S. Jana, L. Watson and C. D. Pilgram, Tetrahedron Lett.,
2008, 49, 5408.
8 (a) M. Yamato, K. Hashigaki, N. Qais and S. Ishikawa, Tetrahedron,
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Chem., 2001, 66, 6926.
9 H. Ardill, X. L. R. Fontaine, R. Grigg, D. Henderson, J. Montgomery,
V. Sridharan and S. Surendrakumar, Tetrahedron, 1990, 46, 6449.
10 Q. Zhang, G. Tu, Y. Zhao and T. Cheng, Tetrahedron, 2002, 58,
6795.
Acknowledgements
We would like to thank the Royal Society for an International
Incoming Fellowship (IIF-2007/R1), the University of Sheffield,
EPSRC and AstraZeneca. We are grateful to Brian Taylor for
NMR spectra and Harry Adams for X-ray crystal structure
analyses.
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Saha, M. J. McKenzie and W. P. Martin, J. Org. Chem., 2007, 72,
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Meyer and T. Opatz, Eur. J. Org. Chem., 2006, 3997; (f) J. Szawkalo,
A. Zawadzka, K. Wojtasiewicz, A. Leniewski, J. Drabowicz and Z.
Czarnocki, Tetrahedron: Asymmetry, 2005, 16, 3619; (g) H.-J. Kno¨lker
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Czarnocki, A. Zawadzka, K. Wojtasiewicz, A. Leniewski, J. K. Maurin,
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Notes and references
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