Intermolecular radical addition and addition/cyclization reactions of alkoxyamines onto nonactivated alkenes

Organic Letters

Volumn 5, Issue 16, 2003, Pages 2899-2902

  Wetter, Christian ^a   Jantos, Katja ^a   Woithe, Katharina ^a   Studer, Armido ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; AMINE; MALONIC ACID DERIVATIVE;

ADDITION REACTION; ARTICLE; BIOAVAILABILITY; CYCLIZATION; FRAGMENTATION REACTION; MOLECULAR INTERACTION; POLYMERIZATION; RADICAL REACTION;

EID: 0141855228     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034994k     Document Type: Article

References (22)

1. Studer, A. Angew. Chem., Int. Ed. 2000, 39, 1108. See also: Allen, D. A. ; Fenwick, M. F.; Henry-Riyad, H.; Tidwell, T. T. J. Org. Chem. 2001, 66, 5759. Leroi, C.; Fenet, B.; Couturier, J.-L.; Guerret, O.; Ciufolini, M. A. Org. Lett. 2003, 5, 1079.
2. Studer, A. Angew. Chem., Int. Ed. 2000, 39, 1108. See also: Allen, D. A. ; Fenwick, M. F.; Henry-Riyad, H.; Tidwell, T. T. J. Org. Chem. 2001, 66, 5759. Leroi, C.; Fenet, B.; Couturier, J.-L.; Guerret, O.; Ciufolini, M. A. Org. Lett. 2003, 5, 1079.
3. Studer, A. Angew. Chem., Int. Ed. 2000, 39, 1108. See also: Allen, D. A. ; Fenwick, M. F.; Henry-Riyad, H.; Tidwell, T. T. J. Org. Chem. 2001, 66, 5759. Leroi, C.; Fenet, B.; Couturier, J.-L.; Guerret, O.; Ciufolini, M. A. Org. Lett. 2003, 5, 1079.
4. (a) Studer, A. Chem. Eur. J. 2001, 7, 1159.
5. (b) Fischer, H. Chem. Rev. 2001, 101, 3581.
6. Camacho, D. H.; Nakamura, I.; Saito, S.; Yamamoto, Y. J. Org. Chem. 2001, 66, 270 and references therein.
7. Clayden, J.; Greeves, N.; Warren, S.; Wothers, P. Organic Chemistry; Oxford University Press: New York, 2001.
8. (a) Nakamura, H.; Sekido, M.; Ito, M.; Yamamoto, Y. J. Am. Chem. Soc. 1998, 120, 6838.
9. (b) Monteiro, N.; Balme, G. Synlett 1998, 746.
10. (c) Fürstner, A.; Szillat, H.; Stelzer, F. J. Am. Chem. Soc. 2000, 122, 6785.
11. Hawker, C. J.; Bosman, A. W.; Hart, E. Chem. Rev. 2001, 101, 3661.
12. Marque, S.; Fischer, H.; Baier, E.; Studer, A. J. Org. Chem. 2001, 66, 1146. See also: Marque, S.; Fischer, H.; LeMercier, C.; Tordo, P. Macromolecules 2000, 33, 4403.
13. Marque, S.; Fischer, H.; Baier, E.; Studer, A. J. Org. Chem. 2001, 66, 1146. See also: Marque, S.; Fischer, H.; LeMercier, C.; Tordo, P. Macromolecules 2000, 33, 4403.
14. Formal long-lived radicals due to degenerate processes: Zard, S. Z. Angew. Chem., Int. Ed. Engl. 1997, 36, 672.
15. Fischer, H.; Radom, L. Angew. Chem., Int. Ed. 2001, 40, 1341.
16. Curran, D. P.; Chen, M.-H.; Spletzer, E.; Seong, C. M.; Chang, C.-T. J. Am. Chem. Soc. 1989, 111, 8872. Review: Byers, J. In Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, 2001; Vol. 1, 72
17. Curran, D. P.; Chen, M.-H.; Spletzer, E.; Seong, C. M.; Chang, C.-T. J. Am. Chem. Soc. 1989, 111, 8872. Review: Byers, J. In Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, 2001; Vol. 1, 72
18. Reactions under the above-described optimized conditions provided lower yields.
19. Diastereoisomers could not be separated. The relative configuration was assigned on the basis of literature reports on similar cyclizations: Amrein, S. ; Studer, A. Helv. Chim. Acta 2002, 85, 3559.
20. Beckwith, A. L. J.; Bowry, V. W.; Ingold, K. U. J. Am. Chem. Soc. 1992, 114, 4983.
21. We currently believe that elimination occurs via an ionic-type process from the corresponding tertiary alkoxyamines. Since C-O bond homolysis in these tertiary alkoxyamines is not efficient, radical disproportionation is less likely. For a discussion, see: Ananchenko, G. S.; Fischer, H. J. Polym. Sci. Part A: Polym. Chem. 2001, 39, 3604.
22. For 34, exomethylene:βγ-unsaturated:γδ -unsaturated = 3.9:1:1.2. For 35, exomethylene:βγ-unsaturated:γ δ-unsaturated = 1.1:1:0.4. The βγ-and γ,δ -unsaturated compounds were obtained as a trans/cis mixture of isomers.