Highly regioselective ring-opening/cross-metathesis reactions of 2-sulfonylnorbornene derivatives

Organic Letters

Volumn 6, Issue 10, 2004, Pages 1625-1627

  Weeresakare, G Mahika ^a   Liu, Zhuqing ^a   Rainier, Jon D ^a  

^a UNIVERSITY OF UTAH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2 SULFONYLNORBORNENE DERIVATIVE; 7 AZANORBORNENE; 7 OXANORBORNENE; NORBORNENE DERIVATIVE; ORGANIC COMPOUND; SULFONE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; MOLECULE; RING OPENING; SUBSTITUTION REACTION;

EID: 2542558884     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol049561b     Document Type: Article

References (29)

1. For recent reviews, see: (a) Grubbs, R. H.; Trnka, T. M.; Sanford, M. S. Curr. Meth. Inorg. Chem. 2003, 3, 187. (b) Connon, S. J.; Blechert, S. Angew. Chem., Int. Ed. 2003, 42, 1900.
2. For recent reviews, see: (a) Grubbs, R. H.; Trnka, T. M.; Sanford, M. S. Curr. Meth. Inorg. Chem. 2003, 3, 187. (b) Connon, S. J.; Blechert, S. Angew. Chem., Int. Ed. 2003, 42, 1900.
3. For a recent review on the use of norbornenes in ROM/CM sequences, see: Arjona, O.; Csákÿ, A. G.; Plumet, J. Eur. J. Org. Chem. 2003, 611.
4. The state of the art in this area is Arjona and Plumet's use of 2-substituted 7-oxanorbornenes to give ca. 4:1 mixtures of tetrahydrofuran regioisomers. See: Arjona, O.; Csákÿ, A. G.; Murcia, M. C.; Plumet, J. J. Org. Chem. 1999, 64, 9739.
5. Other than with the cyclopentadiene dimer, regioselective ROM/CM reactions of 2-substituted norbornenes have not been identified; see: (a) Mayo, P.; Tam, W. Tetrahedron 2002, 58, 9513. (b)
6. For ROM/CM reactions of 2-azanorbornenes, see: (a) Schneider, M. F.; Lucas, N.; Velder, J.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 257. (b) Ishikura, M.; Saijo, M.; Hino, A. Heterocycles 2002, 57, 241.
7. For ROM/CM reactions of 2-azanorbornenes, see: (a) Schneider, M. F.; Lucas, N.; Velder, J.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 257. (b) Ishikura, M.; Saijo, M.; Hino, A. Heterocycles 2002, 57, 241.
8. An alternative is to desymmetrize symmetrical norbornenes. For a recent review that includes a discussion of this topic, see: (a) Hoveyda, A. H.; Schrock, R. R. Angew. Chem., Int. Ed. 2003, 42, 4592.
9. Chelation of heteroatoms to Ru has been proposed to be important in other metathetical processes. See refs 1-3 and: (a) Fürstner, A.; Langemann, K. Synthesis 1997, 792. (b) Paquette, L. A.; Fabris, F.; Tae, J.; Gallucci, J. C.; Hofferberth, J. E. J. Am. Chem. Soc. 2000, 122, 3391. (c) Zaja, M.; Connon, S. J.; Dunne, A. M.; Rivard, M.; Buschmann, N.; Jiricek, J.; Blechert, S. Tetrahedron 2003, 59, 6545.
10. Chelation of heteroatoms to Ru has been proposed to be important in other metathetical processes. See refs 1-3 and: (a) Fürstner, A.; Langemann, K. Synthesis 1997, 792. (b) Paquette, L. A.; Fabris, F.; Tae, J.; Gallucci, J. C.; Hofferberth, J. E. J. Am. Chem. Soc. 2000, 122, 3391. (c) Zaja, M.; Connon, S. J.; Dunne, A. M.; Rivard, M.; Buschmann, N.; Jiricek, J.; Blechert, S. Tetrahedron 2003, 59, 6545.
11. Chelation of heteroatoms to Ru has been proposed to be important in other metathetical processes. See refs 1-3 and: (a) Fürstner, A.; Langemann, K. Synthesis 1997, 792. (b) Paquette, L. A.; Fabris, F.; Tae, J.; Gallucci, J. C.; Hofferberth, J. E. J. Am. Chem. Soc. 2000, 122, 3391. (c) Zaja, M.; Connon, S. J.; Dunne, A. M.; Rivard, M.; Buschmann, N.; Jiricek, J.; Blechert, S. Tetrahedron 2003, 59, 6545.
12. Remote substituent effects on regioselective reactions are well documented with norbornene derivatives; see for example: (a) Black, K. A.; Vogel, P. J. Org. Chem. 1986, 51, 5341. (b) Arjona, O.; Csákÿ, A. G.; Murcia, M. C.; Plumet, J. J. Org. Chem. 1999, 64, 7338. (c) Jordan, R. W.; Tam, W. Org. Lett. 2000, 2, 3031.
13. Remote substituent effects on regioselective reactions are well documented with norbornene derivatives; see for example: (a) Black, K. A.; Vogel, P. J. Org. Chem. 1986, 51, 5341. (b) Arjona, O.; Csákÿ, A. G.; Murcia, M. C.; Plumet, J. J. Org. Chem. 1999, 64, 7338. (c) Jordan, R. W.; Tam, W. Org. Lett. 2000, 2, 3031.
14. Remote substituent effects on regioselective reactions are well documented with norbornene derivatives; see for example: (a) Black, K. A.; Vogel, P. J. Org. Chem. 1986, 51, 5341. (b) Arjona, O.; Csákÿ, A. G.; Murcia, M. C.; Plumet, J. J. Org. Chem. 1999, 64, 7338. (c) Jordan, R. W.; Tam, W. Org. Lett. 2000, 2, 3031.
15. For reviews covering the generation of nitrogen-containing compounds using RCM, see: (a) Walters, M. A. Recent Advances in the Synthesis of Heterocycles via RCM. In Progress in Heterocyclic Chemistry; Gribble, G. W., Joule, J. A., Eds.; Pergamon: Elmsford, NY, 2003; Vol. 15, p 1. (b) Phillips, A. J.; Abell, A. D. Aldrichimica Acta 1999, 32, 75.
16. For reviews covering the generation of nitrogen-containing compounds using RCM, see: (a) Walters, M. A. Recent Advances in the Synthesis of Heterocycles via RCM. In Progress in Heterocyclic Chemistry; Gribble, G. W., Joule, J. A., Eds.; Pergamon: Elmsford, NY, 2003; Vol. 15, p 1. (b) Phillips, A. J.; Abell, A. D. Aldrichimica Acta 1999, 32, 75.
17. Leung,-Toung, R.; Liu, Y.; Muchowski, J. M.; Wu, Y.-L. J. Org. Chem. 1998, 63, 3235.
18. Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 1, 953.
19. Other examples of regioselective ROM/CM reactions include Snapper's cyclobutene ROM/CM reactions; see: (a) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am. Chem. Soc. 1997, 119, 1478. (b) Tallarico, J. A.; Bonitatebus, P. J., Jr.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157.
20. Other examples of regioselective ROM/CM reactions include Snapper's cyclobutene ROM/CM reactions; see: (a) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am. Chem. Soc. 1997, 119, 1478. (b) Tallarico, J. A.; Bonitatebus, P. J., Jr.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157.
21. See refs 1-3 and: Arjona, O.; Csákÿ, A. G.; Plumet, J. Synthesis 2000, 857.
22. In the case of substrates also having bridgehead substitution, Arjona and Plumet observed high levels of regioselectivity but at the expense of low overall conversions. See ref 2.
23. Grubbs has reported that vinyl acetates do not undergo cross-metathesis with 2; see: Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783.
24. For 11-14 and 20, COSY cross-peaks were observed between H(7) and H(6), H(6) and H(5), H(5) and H(4), H(4) and H(3), and H(3) and H(2). For compound 13, NOE enhancements were observed between H(2) and H(5) and between H(5) and H(3).
25. Regiochemistries of pyrrolidines 5 and 7-10 were assigned on the basis of the similarity of their spectra to those of 3, 4, 6, and 11.
26. Lehmizidine alkaloids: Garraffo, H. M.; Jain, P.; Spande, T. F.; Daly, J. W.; Jones, T. H.; Smith, L. J.; Zottig, V. E. J. Nat. Prod. 2001, 64, 421.
27. Stemona alkaloids: Pilli, R. A.; da Conceiçã Ferreira de Oliveira, M. Nat. Prod. Rep. 2000, 17, 117.
28. Azanorbornene 16 was a minor product formed during the generation of 1.
29. Determined following removal of the Boc group and global hydrogenation.