Triethylborane-Induced Radical Allylation Reaction with Zirconocene-Olefin Complex

Organic Letters

Volumn 6, Issue 4, 2004, Pages 593-595

  Hirano, Koji ^a   Fujita, Kazuya ^a   Shinokubo, Hiroshi ^a   Oshima, Koichiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; BORANE DERIVATIVE; CARBON; CARBONYL DERIVATIVE; HALOGEN; REAGENT; TRIETHYLBORANE; UNCLASSIFIED DRUG; ZIRCONIUM DERIVATIVE; ZIRCONOCENE;

ALLYLATION; ARTICLE; CHEMICAL BOND; CHEMICAL STRUCTURE; COMPLEX FORMATION;

EID: 1342332898     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol036431e     Document Type: Article

References (27)

1. (a) Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, 2001.
2. (b) Jasperse, C. P.; Curran, D. P.; Fevig, T. L. Chem. Rev. 1991, 91, 1237.
3. (a) Keck, G. E.; Enholm, E. J.; Yates, J. B.; Wiley, M. R. Tetrahedron 1985, 41, 4079.
4. (b) Curran, D. P. Synthesis 1998, 417 and 489.
5. Bagley, P. A.; Walton, J. C. Angew. Chem., Int. Ed. 1998, 37, 3072.
6. Silicon-based radical chain carriers such as allyl tris(trimethylsilyl)- silane are effective alternatives to tin reagents, although these compounds are often costly. (a) Chatgilialoglu, C.; Ballestri, M.; Vecchi, D.; Curran, D. P. Tetrahedron Lett. 1996, 37, 6383. (b) Chatgilialoglu, C.; Ferreri, C.; Ballestri, M.; Curran, D. P. Tetrahedron Lett. 1996, 37, 6387. (c) Guindon, Y.; Guerin, B.; Chabot, C.; Oglivie, W. J. Am. Chem. Soc. 1996, 118, 12528. (d) Porter, N. A.; Wu, J. H.; Zhang, G.; Reed, A. D. J. Org. Chem. 1997, 62, 6702.
7. Silicon-based radical chain carriers such as allyl tris(trimethylsilyl)- silane are effective alternatives to tin reagents, although these compounds are often costly. (a) Chatgilialoglu, C.; Ballestri, M.; Vecchi, D.; Curran, D. P. Tetrahedron Lett. 1996, 37, 6383. (b) Chatgilialoglu, C.; Ferreri, C.; Ballestri, M.; Curran, D. P. Tetrahedron Lett. 1996, 37, 6387. (c) Guindon, Y.; Guerin, B.; Chabot, C.; Oglivie, W. J. Am. Chem. Soc. 1996, 118, 12528. (d) Porter, N. A.; Wu, J. H.; Zhang, G.; Reed, A. D. J. Org. Chem. 1997, 62, 6702.
8. Silicon-based radical chain carriers such as allyl tris(trimethylsilyl)- silane are effective alternatives to tin reagents, although these compounds are often costly. (a) Chatgilialoglu, C.; Ballestri, M.; Vecchi, D.; Curran, D. P. Tetrahedron Lett. 1996, 37, 6383. (b) Chatgilialoglu, C.; Ferreri, C.; Ballestri, M.; Curran, D. P. Tetrahedron Lett. 1996, 37, 6387. (c) Guindon, Y.; Guerin, B.; Chabot, C.; Oglivie, W. J. Am. Chem. Soc. 1996, 118, 12528. (d) Porter, N. A.; Wu, J. H.; Zhang, G.; Reed, A. D. J. Org. Chem. 1997, 62, 6702.
9. Silicon-based radical chain carriers such as allyl tris(trimethylsilyl)- silane are effective alternatives to tin reagents, although these compounds are often costly. (a) Chatgilialoglu, C.; Ballestri, M.; Vecchi, D.; Curran, D. P. Tetrahedron Lett. 1996, 37, 6383. (b) Chatgilialoglu, C.; Ferreri, C.; Ballestri, M.; Curran, D. P. Tetrahedron Lett. 1996, 37, 6387. (c) Guindon, Y.; Guerin, B.; Chabot, C.; Oglivie, W. J. Am. Chem. Soc. 1996, 118, 12528. (d) Porter, N. A.; Wu, J. H.; Zhang, G.; Reed, A. D. J. Org. Chem. 1997, 62, 6702.
10. (a) Quiclet-Sire, B.; Zard, S. Z. J. Am. Chem. Soc. 1996, 118, 1209.
11. (b) Guyader, F. L.; Quiclet-Sire, B.; Seguin, S.; Zard, S. Z. J. Am. Chem. Soc. 1997, 119, 7410.
12. (c) Sire, B.; Seguin, S.; Zard, S. Z. Angew. Chem., Int. Ed. 1998, 37, 2864.
13. Usugi, S.; Yorimitsu, H.; Oshima, K. Tetrahedron Lett. 2001, 42, 4535.
14. 2Zr(H)Cl-mediated radical reduction reaction involving homolytic cleavage of the zirconium-hydrogen bond: (a) Fujita, K.; Nakamura, T.; Yorimitsu, H.; Oshima, K. J. Am. Chem. Soc. 2001, 123, 3137. (b) Fujita, K.; Yorimitsu, H.; Oshima, K. Synlett 2002, 337.
15. 2Zr(H)Cl-mediated radical reduction reaction involving homolytic cleavage of the zirconium-hydrogen bond: (a) Fujita, K.; Nakamura, T.; Yorimitsu, H.; Oshima, K. J. Am. Chem. Soc. 2001, 123, 3137. (b) Fujita, K.; Yorimitsu, H.; Oshima, K. Synlett 2002, 337.
16. 2ZrCl(2-butenyl).
17. Use of 1.5 equiv of allylzirconium provided 3a in only 34% yield along with the recovered α-iodo ester.
18. (a) Nozaki, K.; Oshima, K.; Utimoto, K. J. Am. Chem. Soc. 1987, 109, 2547.
19. (b) Oshima, K.; Utimoto, K. J. Synth. Org. Chem. Jpn. 1989, 47, 40.
20. 3B, most of the α-bromo ester was recovered along with a trace of the allylation product.
21. (a) Fujita, K.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. J. Am. Chem. Soc. 2001, 123, 12115.
22. (b) Fujita, K.; Shinokubo, H.; Oshima, K. Angew. Chem., Int. Ed. 2003, 42, 2550.
23. (c) Fujita, K.; Shinokubo, H.; Oshima, K. J. Org. Chem. Submitted for publication.
24. In general, the radical allylation of tertiary bromides provides the desired products in poor yields due to the steric effect.
25. Failure of reaction with crotylstannane can be attributed to the reduced reactivity of crotylstannane and the isomerization to more reactive 3-buten-2-ylstannane. (a) Clive, D. L. J.; Psul, C. C.; Wang, Z. J. Org. Chem. 1997, 62, 7028. Sibi has developed selective crotylation of α-carbonyl radicals at low temperatures with a Lewis acid catalyst. (b) Sibi, M. P.; Chen, J. J. Am. Chem. Soc. 2001, 123, 9427. (c) Sibi, M. P.; Miyabe, H. Org. Lett. 2002, 4, 3435.
26. Failure of reaction with crotylstannane can be attributed to the reduced reactivity of crotylstannane and the isomerization to more reactive 3-buten-2-ylstannane. (a) Clive, D. L. J.; Psul, C. C.; Wang, Z. J. Org. Chem. 1997, 62, 7028. Sibi has developed selective crotylation of α-carbonyl radicals at low temperatures with a Lewis acid catalyst. (b) Sibi, M. P.; Chen, J. J. Am. Chem. Soc. 2001, 123, 9427. (c) Sibi, M. P.; Miyabe, H. Org. Lett. 2002, 4, 3435.
27. Failure of reaction with crotylstannane can be attributed to the reduced reactivity of crotylstannane and the isomerization to more reactive 3-buten-2-ylstannane. (a) Clive, D. L. J.; Psul, C. C.; Wang, Z. J. Org. Chem. 1997, 62, 7028. Sibi has developed selective crotylation of α-carbonyl radicals at low temperatures with a Lewis acid catalyst. (b) Sibi, M. P.; Chen, J. J. Am. Chem. Soc. 2001, 123, 9427. (c) Sibi, M. P.; Miyabe, H. Org. Lett. 2002, 4, 3435.