Synthesis and Ring-Opening Cross Metathesis of Bicyclo[3.2.1]oct-6-en-3-ones
FULL PAPERS
(m, 2H), 5.60–5.80 (m, 1H); 13C NMR (50 MHz, CDCl3; E-iso-
mer): d¼13.8 (q), 22.1 (t), 31.5 (t), 32.1 (t), 38.1 (t), 40.6 (d),
41.3 (d), 46.5 (t), 47.4 (t), 113.5 (t), 129.9 (d), 132.8 (d), 141.2
(d), 210.3 (s); (Z-isomer): d¼13.8 (q), 22.1 (t), 27.1 (t), 31.9
(t), 38.1 (t), 38.1 (d), 41.5 (d), 46.5 (t), 47.4 (t), 113.5 (t), 130.0
(d), 132.2 (d), 141.2 (d), 210.2 (s).
[4] a) M. D. Mihovilovic, F. Rudroff, W. Kandioller, B.
Grçtzl, P. Stanetty, H. Spreitzer, Synlett 2003, 1973–
1976; b) M. D. Mihovilovic, B. Mꢁller, M. M. Kayser,
J. D. Stewart, J. Frçhlich, P. Stanetty, H. Spreitzer, J.
Mol. Catal. B: Enzym. 2001, 11, 349–353.
[5] M. D. Mihovilovic, B. Mꢁller, M. M. Kayser, P. Stanetty,
Synlett 2002, 700–702.
[6] H. M. R. Hoffmann, Angew. Chem. 1984, 96, 29–58.
[7] A. W. Fort, J. Am. Chem. Soc. 1962, 84, 4979–4981.
[8] A. M. Montana, P. M. Grima, Synth. Commun. 2003, 33,
265–279 and references cited therein.
[9] R. Dunkel, H. M. R. Hoffmann, Tetrahedron 1999, 55,
8385–8396 and references cited therein.
[10] R. Noyori, Acc. Chem. Res. 1979, 12, 61–66.
[11] F. Carrel, P. Vogel, Tetrahedron: Asymmetry 2000, 11,
4661–4680.
[12] T. Sato, R. Noyori, Bull. Chem. Soc. Jpn. 1978, 51, 2745–
2746.
[13] H. M. R. Hoffmann, H. Kim, Eur. J. Org. Chem. 2000,
2195–2201.
cis-5-Ethenyl-3-(2’-phenyl-1’-ethenyl)-cyclohexan-1-one
(6e): Conversion with styrene according to the above general
1
protocol gave 6e as a colorless oil; yield: 113 mg (61%); H
NMR (200 MHz, CDCl3): d¼1.37–1.56 (m, 1H), 2.04–2.57
(m, 7H), 5.00–5.10 (m, 2H), 5.73–5.90 (m, 1H), 6.08–6.19
(dd, J¼6.8 Hz, J¼9 Hz, 1H,), 6.40 (d, J¼15.8 Hz, 1H), 7.21–
7.37 (m, 5H); 13C-NMR (50 MHz, CDCl3): d¼37.8 (t), 40.9
(d), 41.3 (d), 46.5 (t), 46.9 (t), 113.8 (t), 126.1 (d), 127.4 (d),
128.6 (d), 129.1 (d), 132.7 (d), 136.9 (d), 141.0 (d), 209.7 (s).
cis-5-Ethenyl-3-(3’-phenyl-1’-propenyl)-cyclohexan-1-one
(6f): Conversion with allylbenzene according to the above gen-
eral protocol gave 6f as a colorless oil; yield: 98 mg (50%); 1H
NMR (200 MHz, CDCl3; E/Z-isomers): d¼1.16–1.45 (m,
1H), 1.65–2.55 (m, 6H), 2.81–2.85 (m, 1H), 3.25–3.34 (m,
2H), 4.91–5.01 (m, 2H), 5.23–5.34 (m, 1H), 5.35–5.56 (m,
1H), 5.63–5.80 (m, 1H), 7.06–7.25 (m, 5H); 13C NMR
(50 MHz, CDCl3; E-isomer): d¼33.6 (t), 36.2 (d), 38.4 (t),
40.5 (d), 47.2 (t), 47.3 (t), 113.6 (t), 126.1 (d), 128.2 (d), 128.3
(d), 128.4 (d), 134.3 (d), 141.1 (d), 209.9 (s); (Z-isomer): d¼
33.6 (t), 36.2 (d), 37.9 (t), 41.3 (d), 47.2 (t), 47.3 (t), 113.6 (t),
126.1 (d), 128.2 (d), 128.3 (d), 128.4 (d), 133.3 (d), 140.1 (d),
209.8 (s).
[14] A. M. Montana, P. M. Grima, Tetrahedron Lett. 2001, 42,
7809–7813.
[15] For an excellent review, see: D. H. Bremner, Ultrason.
Sonochem. 1994, 1, 119–124.
[16] For recent reviews see: a) K. C. Nicolaou, P. G. Bulger,
D. Sarlah, Angew. Chem. 2005, 117, 4564–4601;
b) R. H. Grubbs, Tetrahedron 2004, 60, 7117–7140;
c) R. H. Grubbs, in: Handbook of Metathesis, Wiley-
VCH, Weinheim, 2003, Vols. 1 and 2; d) A. Fꢁrstner, An-
gew. Chem. Int. Ed. 2000, 39, 3012–3043; c) R. H.
Grubbs, S. Chang, Tetrahedron 1998, 54, 4413–4450.
[17] For reviews on RCM, see: a) F.-X. Felpin, J. Lebreton,
Eur. J. Org. Chem. 2003, 3693–3712; b) P. V. Ramachan-
dran, M. V. R. Reddy, H. C. Brown, Pure Appl. Chem.
2003, 75, 1263–1275; c) J. Prunet, Angew. Chem. Int.
Ed. 2003, 42, 2826–2830.
[18] a) G. M. Weeresakare, Z. Liu, J. D. Rainier, Org. Lett.
2004, 6, 1625–1627; b) S. J. Connon, S. Blechert, Angew.
Chem. Int. Ed. 2003, 42, 1900–1923; c) G. Hofle, N. Glas-
er, T. Leibold, U. Karama, F. Sasse, H. Steinmetz, Pure
Appl. Chem. 2003, 75, 167–178.
Acknowledgements
Fundingfor this project in part by the European Commission
under the Human Potential Program of FP-5 (contract no.
HPMT-CT-2001-00243 – Marie-Curie TrainingSite GEMCAT)
and the Austrian Science Fund (FWF, project no. P16373) is
gratefully acknowledged. D.A.B. thanks Fundacion Anforchas
(project no. 14308/92) for financial support. The authors would
like to thank Prof. Marc Snapper (Merkert Chemistry Center,
Boston College) and Prof. Jon D. Stewart (University of Flori-
da) for valuable suggestions.
[19] a) M. L. Randall, J. A. Tallarico, M. L. Snapper, J. Am.
Chem. Soc. 1995, 117, 9610–9611; b) M. L. Randall,
J. A. Tallarico, M. L. Snapper, J. Am. Chem. Soc. 1997,
119, 1478–1479; c) J. A. Tallarico, P. J. Bonitatebus,
M. L. Snapper, J. Am. Chem. Soc. 1997, 119, 7157–7158.
[20] M. F. Schneider, S. Blechert, Angew. Chem. Int. Ed. 1996,
35, 411–412.
References and Notes
[1] a) M. D. Mihovilovic, F. Rudroff, B. Grçtzl, Curr. Org.
Chem. 2004, 8, 1057–1069; b) N. M. Kamerbeek, D. B.
Janssen, W. J. H. van Berkel, M. W. Fraaije, Adv. Synth.
Catal. 2003, 345, 667–678; c) M. D. Mihovilovic, B. Mꢁl-
ler, P. Stanetty, Eur. J. Org. Chem. 2002, 3711–3730.
[2] For an excellent review in biocatalytic desymmetrization
reactions, see: E. Garcia-Urdiales, I. Alfonso, V. Gotor,
Chem. Rev. 2005, 105, 313–354.
[3] a) M. D. Mihovilovic, F. Rudroff, B. Grçtzl, P. Kapitan,
R. Snajdrova, J. Rydz, R. Mach, Angew. Chem. Int. Ed.
2005, 44, 3609–3613; b) M. D. Mihovilovic, F. Rudroff,
B. Mꢁller, P. Stanetty, Bioorg. Med. Chem. Lett. 2003,
13, 1479–1482; c) M. D. Mihovilovic, G. Chen, S. Wang,
B. Kyte, F. Rochon, M. M. Kayser, J. D. Stewart, J. Org.
Chem. 2001, 66, 733–738.
[21] D. L. Wright, L. C. Usher, M. Estrella-Jimenez; Org.
Lett. 2001, 3, 4275–4277.
[22] J. J. Van Veldhuizen, J. E. Campbell, R. E. Giudici; A. H.
Hoveyda J. Am. Chem. Soc. 2005, 127, 6877–6882.
[23] For a preceding non-chiral version of this transforma-
tion, see: D. G. Gillingham, O. Kataoka, S. B. Garber,
A. H. Hoveyda J. Am. Chem. Soc. 2004, 126, 12288–
12290.
[24] C. Rappe, Arkiv Kemi 1963, 21, 503–516.
[25] The Cu/Zn couple was prepared by the procedure of E.
LeGoff, J. Org. Chem. 1964, 29, 2048–2050.
Adv. Synth. Catal. 2006, 348, 463 – 470
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