Free radical addition to branched allylsilanes: Stereoselective formation and elimination of β bromosilanes

Tetrahedron Letters

Volumn 41, Issue 31, 2000, Pages 5773-5777

  Porter, Ned A ^a,b   Zhang, Guiru ^a,b   Reed, Aimee D ^b  

^a VANDERBILT UNIVERSITY   (United States)

^b DUKE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACID; BROMINE DERIVATIVE; FREE RADICAL; SILANE DERIVATIVE;

ARTICLE; CATALYSIS; DIASTEREOISOMER; REACTION ANALYSIS; REACTION TIME; STEREOCHEMISTRY; SYNTHESIS;

EID: 0034729918     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(00)00902-3     Document Type: Article

References (17)

1. Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim, 1995.
2. Sibi, M.; Porter, N. A. Acc. Chem. Res. 1999, 32, 163.
3. (b) Wu, J. H.; Radinov, R.; Porter, N. A. J. Am. Chem. Soc. 1995, 117, 11029.
4. (c) Sibi, M. P.; Ji, J.; Wu, J. H.; Gürtler, S.; Porter, N. A. J. Am. Chem. Soc. 1996, 118, 9200.
5. (c) Nanni, D.; Curran, D. P. Tetrahedron: Asymmetry 1996, 8, 2417.
6. Guindon, Y.; Guerin, B.; Chabot, C.; Ogilvie, W. J. Am. Chem. Soc. 1996, 118, 12528.
7. (a) Sibi, M. P.; Jasperse, C. P.; Ji, J. J. Am. Chem. Soc. 1995, 117, 10779.
8. (b) Renaud, P.; Gerster, M. J. Am. Chem. Soc. 1995, 117, 6607.
9. The allylic (crotyl) isomer is formed in less than 2% by the use of the Wittig methodology.
10. Ager, D. J.; Fleming, I.; Patel, S. K. J. Chem. Soc., Perkin Trans. 1 1981, 2520.
11. In those cases where the starting allylsilane was contaminated with the allylic isomer, the crotyl silane reacted much more slowly than 2 did. Use of excess silane gave products containing insignificant amounts of the allylic isomer of 5.
12. 13C spectrum from that of the trans-isomer.
13. 4. The products were purified by flash column chromatography on silica gel (85:15 hexanes:EtOAc) to give the products as a mixture of cis:trans alkenes.
14. 2=7.2 Hz).
15. The phenylselinide product 4b is converted to the alkene 5 on silica that has not been deactivated.
16. See, for example: Giese, B.; Damm, W.; Dickhaut, J.; Wetterich, F.; Sun, S.; Curran, D. P. Tetrahedron Lett. 1991, 32, 6097.
17. Jarvis, A. W. P.; Holt, P.; Tompson, J. J. Chem. Soc. (B) 1970, 746.