566
R. Ben-Othman et al. / Tetrahedron 64 (2008) 559e567
Chem. Rev. 2004, 104, 2199; (m) Katz, T. J. Angew. Chem., Int. Ed.
2005, 44, 3010; (n) Furstner, A.; Davies, P. W. Chem. Commun. 2005,
4.12. 9b-Ethyl-2-vinyl-3,9b-dihydropyrrolo[2,1-a]-
isoindol-5-one (16)
¨
2307; (o) Mori, M. J. Synth. Org. Chem. Jpn. 2005, 63, 423; (p) Nicolaou,
K. C.; Bulger, P. G.; Sarlah, D. Angew. Chem., Int. Ed. 2005, 44, 4490.
2. For reviews on enyne metathesis, see: (a) Poulsen, C. S.; Madsen, R.
Synthesis 2003, 1; (b) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004,
104, 1317; (c) Mori, M. J. Mol. Catal. A: Chem. 2004, 213, 73; For recent
We have used the same protocol, which was described in the
preparation of 6aed. The eluent used for the flash chromatogra-
phy was dichloromethane/acetone (95:5). Yellow solid; yield:
73%; mp 72e74 ꢀC; IR (n, cmꢁ1, CHCl3) 1689.8; H NMR
1
€
examples, see: (d) Royer, F.; Vilain, C.; Elkaım, L.; Grimaud, L. Org. Lett.
2003, 5, 2007; (e) Kaliappan, K. P.; Nandurdikar, R. S. Chem. Commun.
2004, 2506; (f) Funel, J.-A.; Prunet, J. J. Org. Chem. 2004, 69, 4555;
(g) Kummer, D. A.; Brenneman, J. B.; Martin, S. F. Org. Lett. 2005, 7,
(200 MHz, CDCl3, 25 ꢀC) d 0.74 (t, J¼7.8 Hz, 3H), 1.90 (q,
J¼7.8 Hz, 2H), 4.02 (dd, J¼2.3, 14.8 Hz, 1H), 4.71 (d, J¼
14.8 Hz, 1H), 5.24e5.12 (m, 2H), 5.94 (s, 1H), 6.43 (dd, J¼
10.9, 18.0 Hz, 1H), 7.33e7.58 (m, 3H), 7.78 (d, J¼7.7 Hz,
´
4621; (h) Gonzalez-Gomez, A.; Dominguez, G.; Perez-Castells, J. Tetra-
hedron Lett. 2005, 46, 7267; (i) Mori, M.; Wakamatsu, H.; Tonogaki, K.;
Fujita, R.; Kitamura, T.; Sato, Y. J. Org. Chem. 2005, 70, 1066.
13
1H); C NMR (50 MHz, CDCl3, 25 ꢀC) d 9.4 (CH3), 32.7
3. See: (a) Heerding, D. A.; Takata, D. T.; Kwon, C.; Huffman, W. F.;
Samanen, J. Tetrahedron Lett. 1998, 39, 6815; (b) Mori, M.; Sakakibara,
N.; Kinoshita, A. J. Org. Chem. 1998, 63, 6082; (c) Schurer, S. C.; Blechert,
(CH2), 51.1 (CH2), 80.9 (Cq), 118.3 (CH2), 122.5 (CH), 125.4
(CH), 129.2 (CH), 130.5 (CH), 131.4 (CH), 133.3 (CH), 142.6
(2Cq), 151.3 (Cq), 176.2 (C]O); LRMS m/z 225 (Mþ , 2),
ꢂ
S. Tetrahedron Lett. 1999, 40, 1877; (d) Schurer, S. C.; Blechert, S. Chem.
¨
Commun. 1999, 1203; (e) Hoye, T. R.; Donaldson, S. M.; Vos, T. J. Org.
Lett. 1999, 1, 277; (f) Bentz, D.; Laschat, S. Synthesis 2000, 1766; (g)
Kinoshita, A.; Sakakibara, N.; Mori, M. Tetrahedron 1999, 55, 8155; (h)
Lane, C.; Snieckus, V. Synlett 2000, 1294; (i) Moreno-Manas, M.; Pleixats,
R.; Santamaria, A. Synlett 2001, 1784; (j) Rosillo, M.; Casarrubios, L.;
197 (96), 196 (base). Anal. Calcd for C15H15NO (225.29): C,
79.97; H, 6.71; N, 6.22. Found: C, 80.39; H, 7.03; N, 6.55.
4.13. DielseAlder adduct (19)
´
Dominguez, G.; Perez-Castells, J. Tetrahedron Lett. 2001, 42, 7029; (k)
Kitamura, T.; Mori, M. Org. Lett. 2001, 3, 1161; (l) Duboc, R.; Henaut,
C.; Savignac, M.; Genet, J. P.; Bhatnagar, N. Tetrahedron Lett. 2001, 42,
2461; (m) Banti, D.; North, M. Tetrahedron Lett. 2002, 43, 1561; (n)
Guo, H.; Madhushaw, R. J.; Shen, F.-M.; Liu, R.-S. Tetrahedron 2002,
58, 5627; (o) Saito, N.; Sato, Y.; Mori, M. Org. Lett. 2002, 4, 803; (p)
Lee, H.-Y.; Kim, H. Y.; Tae, H.; Kim, B. G.; Lee, J. Org. Lett. 2003, 5,
3439; (q) Imhof, S.; Blechert, S. Synlett 2003, 609; (r) Rosillo, M.; Casar-
We have used the same protocol, which was described in
the preparation of 18. The eluent used for the flash chromatog-
raphy was the mixture of cyclohexane/EtOAc (30:70). White
solid; yield: 73%; mp 232e234 ꢀC; IR (n, cmꢁ1, CHCl3)
1
1686.1, 1686.8, 1683.3; H NMR (200 MHz, CDCl3, 25 ꢀC)
d 0.57 (t, J¼7.0 Hz, 3H), 1.90e2.05 (m, 2H), 2.21e2.45 (m,
1H), 2.65e2.72 (m, 1H), 2.76 (dd, J¼15.65, J¼7.83 Hz, 1H),
3.23 (t, J¼8.61 Hz, 1H), 3.46 (dd, J¼3.91, 8.61 Hz, 1H), 3.98
(dt, J¼2.3, 16.4 Hz, 1H), 4.61 (dt, J¼2.3, 16.4 Hz, 1H), 5.78e
5.81 (m, 1H), 6.87e7.03 (m, 2H), 7.61e7.12 (m, 6H), 7.82 (d,
´
rubios, L.; Dominguez, G.; Perez-Castells, J. J. Org. Chem. 2004, 69, 2084;
(s) Kitamura, T.; Kuzuba, Y.; Sato, Y.; Wakamatsu, H.; Fujita, R.; Mori, M.
Tetrahedron 2004, 60, 7375; (t) Ma, S.; Ni, B.; Liang, Z. J. Org. Chem.
2004, 69, 6305; (u) Tae, J.; Hahn, D. W. Tetrahedron Lett. 2004, 45,
3757; (v) Mori, M.; Wakamatsu, H.; Saito, N.; Sato, Y.; Narita, R.; Sato,
Y.; Fujita, R. Tetrahedron 2006, 62, 3872.
13
J¼7.0 Hz, 1H); C NMR (50 MHz, CDCl3, 25 ꢀC) d 8.2
4. (a) Elbein, A. D. Annu. Rev. Biochem. 1987, 56, 497; (b) Fellows, L. E.;
Nash, R. J.; Simmonds, M. S. J.; Scotfield, A. M. Plant Nitrogen Meta-
bolism; Pulton, J. E., Romero, J. T., Conn, E. E., Eds.; Plenum: New
York, NY, 1989; p 395; (c) Leger, G. Adv. Carbohydr. Chem. Biochem.
1999, 48, 319; (d) El Nemr, A. Tetrahedron 2000, 56, 8579; (e) Ostrander,
G. K.; Scribner, N. K.; Rohrschneider, L. T. Cancer Res. 1988, 48, 1091;
(f) Elbein, A. D.; Tropea, J. E.; Molyneux, R. J. U.S. Patent Appl. US
289,907, 1989; Chem. Abstr. 1990, 113, P91444p; (g) Nash, R. J.;
Fellows, L. E. PCT Int. Appl. WO GB Appl. 89/7,951, 1990; Chem.
Abstr. 1990, 114, 143777f.
(CH3), 27.2 (CH2), 35.1 (CH2), 40.6 (CH), 43.1 (CH), 44.4
(CH2), 47.7 (CH), 74.2 (Cq), 117.7 (CH), 121.4 (CH), 124.4
(CH), 126.5 (2CH), 128.5 (CH), 128.6 (CH), 129.2 (2CH),
131.5 (CH), 131.7 (Cq), 136.8 (Cq), 146.6 (Cq), 147.3 (Cq),
170.3 (C]O), 174.1 (C]O), 178.4 (C]O). Anal. Calcd for
C25H22N2O3 (398.47): C, 75.36; H, 5.75; N, 7.03. Found: C,
75.73; H, 6.03; N, 7.32.
5. (a) Tranchant, M. J.; Moine, C.; Ben Othman, R.; Bousquet, T.; Othman,
M.; Dalla, V. Tetrahedron Lett. 2006, 47, 4477; (b) Ben Othman, R.;
Fousse, A.; Bousquet, T.; Othman, M.; Dalla, V. Org. Lett. 2005, 7,
2825; (c) Ben Othman, R.; Bousquet, T.; Othman, M.; Dalla, V.
Acknowledgements
The authors are grateful to Dr. Elizabeth A. Hillard
(ENSCP) and Dr. Vincent Dalla (URCOM) for many fruitful
discussions throughout the course of this work.
´
´
Org. Lett. 2005, 7, 5335; (d) Akue-Gedu, R.; Al Akoum Ebrik, S.;
Witczak-Legrand, A.; Fasseur, D.; El Ghammarti, S.; Couturier, D.;
Decroix, B.; Othman, M.; Debacker, M.; Rigo, B. Tetrahedron 2002,
58, 9239.
References and notes
6. (a) Othman, M.; Pigeon, P.; Decroix, B. Tetrahedron 1998, 54, 8737; (b)
Othman, M.; Decroix, B. Synth. Commun. 1996, 26, 2803.
7. Kim, D. C.; Yoon, W. H.; Choi, H.; Kim, D. H. J. Heterocycl. Chem. 1993,
30, 1431.
1. For recent reviews on metathesis, see: (a) Grubbs, R. H.; Miller, S. J.; Fu,
G. C. Acc. Chem. Res. 1995, 28, 446; (b) Schuster, M.; Blechert, S.
Angew. Chem., Int. Ed. 1997, 36, 2036; (c) Grubbs, R. H.; Chang, S.
Tetrahedron 1998, 54, 4413; (d) Armstrong, S. K. J. Chem. Soc., Perkin
Trans. 1 1998, 371; (e) Phillips, A. J.; Abell, A. D. Aldrichimica Acta
8. (a) Mori, M.; Kitamura, T.; Sakakibara, N.; Sato, Y. Org. Lett. 2000, 2,
543; (b) see Refs. 3i and 3q.
9. 5-Membered ring formation: (a) see Ref. 3e; 6-Membered ring formation:
(b) Leeuwenburg, M. A.; Kulker, C.; Duynstee, H. I.; Overkleeft, H. S.;
van der Marel, G. A.; Van Boom, J. H. Tetrahedron 1999, 55, 8253;
(c) Clark, J. S.; Hamelin, O. Angew. Chem., Int. Ed. 2000, 39, 372;
(d) see Ref. 3k; 7-Membered ring formation: (e) see Ref. 3j; (f) Desroy,
N.; Robert-Peillard, F.; Toueg, J.; Henaut, C.; Duboc, R.; Rager,
M. N.; Savignac, M.; Genet, J. P. Synthesis 2004, 2665; (g) Desroy, N.;
1999, 32, 75; (f) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012;
¨
(g) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18; (h) Schrock,
R. R. Tetrahedron 1999, 55, 8141; (i) Hoveyda, A. H.; Schrock, R. R.
Chem.dEur. J. 2001, 7, 945; (j) Connon, S. J.; Blechert, S. Angew.
Chem., Int. Ed. 2003, 42, 1900; (k) Schrock, R. R.; Hoveyda, A. H.
Angew. Chem., Int. Ed. 2003, 42, 4592; (l) Deiters, A.; Martin, S. F.