T. Honda et al. / Tetrahedron Letters 45 (2004) 5211–5213
5213
Chem., Int. Ed. 1997, 36, 2036–2056; (d) Armstrong, S. K.
J. Chem. Soc., Perkin Trans. 1 1998, 371–388; (e) Grubbs,
R. H.; Chang, S. Tetrahedron 1998, 54, 4413–4450; (f)
Schlock, R. R. Tetrahedron 1999, 55, 8141–8153; (g)
Phillips, A. J.; Abell, A. D. Aldrichim. Acta 1999, 32, 75–
optical rotation of the synthesized compound 1 {½a
+1113 (c 1.00, EtOH), lit.,1 ½aD +1085 (EtOH), lit.,2 ½a
D
D
+990 (c 0.98, EtOH)} and its spectroscopic data15 were
in agreement with those reported.
€
90; (h) Furstner, A. Angew. Chem., Int. Ed. 2000, 39,
In summary, we were able to establish the first diaste-
reoselective chiral synthesis of viroallosecurinine 1 by
employing a tandem RCM of the dienyne system as a
key reaction. In this synthesis, we found that the intra-
molecular cyclization of allyl bromide took place either
3012–3043; (i) Trnka, T. M.; Grubbs, R. H. Acc. Chem.
Res. 2001, 34, 18–29; (j) Hoveyda, A. H.; Schrock, R. R.
Chem. Eur. J. 2001, 7, 945–950; (k) Schrock, R. R.;
Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, 4592–
4633.
7. Metathesis for enyne systems, see: Kinoshita, A.; Mori, M.
J. Org. Chem. 1996, 61, 8356–8357; Kim, S.-H.; Bowden,
N.; Grubbs, R. H. J. Am. Chem. Soc. 1994, 116, 10801–
10802; Kim, S.-H.; Zuercher, W. J.; Bowden, N. B.;
Grubbs, R. H. J. Org. Chem. 1996, 61, 1073–1081.
8. Honda, T.; Namiki, H.; Kaneda, K.; Mizutani, H. Org.
Lett. 2004, 6, 87–89.
through
a SN2and/or S N1 reaction mechanism
depending on the reaction conditions employed. This
methodology is obviously applicable to the synthesis of
other Securinega alkaloids, such as norsecurinine and so
on.
9. Tramontini, M. Synthesis 1982, 604–644.
10. The stereochemistry of the product was determined by its
transformation into the final compound.
Acknowledgements
11. When this reaction was carried out in the absence of
cerium chloride, the optical rotation of the product was
This work was supported in part by a grant from the
Ministry of Education, Culture, Sports, Science and
Technology of Japan.
½a +68.4 (c 1.00, CHCl3). On the other hand, the pure
D
compound has ½a +87.9 (c 1.00, CHCl3).
D
12. Haight, A. R.; Stoner, E. J.; Peterson, M. J.; Grover, V. K.
J. Org. Chem. 2003, 68, 8092–8096.
13. (a) Grela, K.; Harutyunyan, S.; Michrewska, A. Angew.
Chem., Int. Ed. 2002, 41, 4039–4040; styrene ether ruthe-
nium catalyst, see: (b) Kingsbury, J. S.; Harrity, J. P. A.;
Bonitatebus, P. J., Jr.; Hoveyda, A. H. J. Am. Chem. Soc.
1999, 121, 791–799; (c) Garber, S. B.; Kingsbury, J. S.;
Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122,
8168–8179; (d) Hoveyda, A. H.; Gillingham, D. G.; Van
Veldhuizen, J. J.; Kataoka, O.; Garber, S. B.; Kingsbury,
J. S.; Harrity, P. A. Org. Biomol. Chem. 2004, 2, 1–16.
14. Salmond, W. G.; Barta, M. A.; Havens, J. L. J. Org.
Chem. 1978, 43, 2057.
References and notes
1. (a) Saito, S.; Iwamoto, T.; Tanaka, T.; Matsumura, C.;
Sugimoto, N.; Horii, Z.; Tamura, Y. Chem. Ind. 1964,
1263–1264; (b) Saito, S.; Tanaka, T.; Iwamoto, T.;
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1133.
2. Mensah, J. L.; Gleye, J.; Moulis, C.; Fouraste, I. J. Nat.
Prod. 1988, 51, 1113–1115.
15. Selected data for 1: mp 145–147 °C (pale yellow needle,
3. Lajis, N. H.; Guan, O. B.; Sargent, M. V.; Skelton, B. W.;
White, A. H. Aust. J. Chem. 1992, 45, 1893–1897.
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6. For reviews on catalytic metathesis, see: (a) Grubbs, R.
H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446–
452; (b) Schrnalz, H.-G. Angew. Chem., Int. Ed. Engl.
1995, 34, 1833–1836; (c) Schuster, M.; Blechert, S. Angew.
recrystallized from hexane–acetone); ½a +1113 (c 1.0,
D
EtOH). 1H NMR (CDCl3) d 1.07–1.50 (3H, m), 1.62–1.75
(3H, m), 1.93 (1H, d, J ¼ 9:7 Hz), 2.69 (1H, dd, J ¼ 4:3,
9.7 Hz), 2.74–2.78 (2H, m), 3.67 (1H, dd, J ¼ 3:3,
13.0 Hz), 3.91 (1H, dd, J ¼ 4:6, 4.8 Hz), 5.73 (1H, s),
6.65 (1H, d, J ¼ 9:1 Hz), 6.82(1H, dd, J ¼ 5:3, 9.1 Hz);
13C NMR (CDCl3) d 18.4, 21.0, 22.1, 42.6, 43.6, 58.8, 60.7,
91.7, 109.0, 122.7, 148.6, 167.4, 172.8; IR (thin film) 1756,
1632, 1460, 1448, 1375, 1318, 1292, 1260, 1178, 1118, 1096,
1077, 960, 908, 802cm ꢀ1; HRMS m=z found: 217.1100
(calcd for C13H15NO2: 217.1103).