Rearrangement of homoallylic alcohols induced by DAST

Organic Letters

Volumn 8, Issue 10, 2006, Pages 2091-2094

  Canova, Sophie ^a   Bellosta, Véronique ^a   Mignani, Serge ^b   Bigot, Antony ^b   Cossy, Janine ^a  

^a CNRS   (France)

^b SANOFI   (France)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33744779402     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol060529m     Document Type: Article

References (26)

1. (a) Biomedicinal Aspects of Fluorine Chemistry; Filler, R., Kobayashi, Y., Eds.; Elsevier: Amsterdam, 1982.
2. (b) Mann, J. Chem. Soc. Rev. 1987, 16, 381-436.
3. (c) Welch, J. T. Tetrahedron 1987, 43, 3123-3197.
4. (d) Welch, J. T.; Eswarakrishnan, S. Fluorine in Bioorganic Chemistry; Wiley: New York, 1991.
5. (e) Selective Fluorination in Organic and Bioorganic Chemistry; Welch, J. T., Ed.; ACS Symposium Series 456; American Chemical Society: Washington, DC, 1991.
6. (f) Abeles, R. H.; Alston, T. A. J. Biol. Chem. 1990, 265, 16705-16708.
7. (g) Special issue on fluorine chemistry. Tetrahedron: Asymmetry 1994, 5, 955-1126.
8. (h) O'Hagan, D.; Rzepa, H. S. Chem. Commun. 1997, 645-652.
9. (a) Singh, R. P.; Shreeve, J. M. Synthesis 2002, 2561-2578.
10. (b) Hudlický, M. Org. React. 1988, 35, 513-637.
11. Zhou, G.-C.; Zhu, D.-Y. Bioorg. Med. Chem. Lett. 2000, 10, 2055-2057.
12. (a) Vera-Ayoso, Y.; Borrachero, P.; Cabrera-Escribano, F.; Carmona, A. T.; Gómez-Guillén, M. Tetrahedron: Asymmetry 2004, 75, 429-444.
13. (b) Boiadjiev, S. E.; Lightner, D. A. J. Org. Chem. 1997, 62, 399-404.
14. (c) Giannini, G.; Marzi, M.; Moretti, G. P.; Penco, S.; Tinti, M. O.; Pesci, S.; Lazzaro, F.; De Angelis, F. Eur. J. Org. Chem. 2004, 2411-2420.
15. (d) Shiuey, S.-J.; Kulesha, I.; Baggiolini, E. G.; Uskoković, M. R. J. Org. Chem. 1990, 55, 243-247.
16. (e) Burnell-Curty, C.; Faghih, R.; Pagano, T.; Henry, R. F.; Lartey, P. A. J. Org. Chem. 1996, 61, 5153-5154.
17. Middleton, W. J. J. Org. Chem. 1975, 40, 574-578.
18. The unsaturated aldehydes 14-21 formed during the rearrangement process could not be purified because of their instability. β,γ-Unsaturated aldehydes 14, ent-16, and 18-21 were directly reduced into the corresponding primary alcohols 22-27 which were fully characterized.
19. When less than 5 equiv was used, low conversion was observed possibly due to DAST decomposition during the reaction.
20. The isomerization of the double bond of the β,γ-unsaturated aldehydes ent-14, 16, and ent-16 leading to the conjugated aldehyde 15 and 17 was impossible to avoid. For compounds 18-21, the isomerization of the double bond seems to take place much more slowly and was avoided by controlling the treatment with silica gel.
21. In the case of the silyl protecting group, no deprotection was observed in the presence of DAST. See, for example: Shiuey, S. J.; Kulesha, I.; Baggiolini, E. G.; Uskokovic, M. R. J. Org. Chem. 1990, 55, 243-246.
22. 3)): Tanaka, D.; Yoshino, T.; Kouno, I.; Miyashita, M.; Irie, H. Tetrahedron 1993, 49, 10253-10262.
23. Scholl, M.; Ding, S.; Woo Lee, S.; Grubbs, R. H. Org. Lett. 1999, 1, 953-956.
24. 3)), is consistent with more than 75% ee, confirming a good transfer of chirality. For the lactone of (S) configuration, see ref 9.
25. Mulzer, J.; Kattner, L.; Strecker, A. R.; Schröder, C.; Bushmann, J.; Lehmann, C.; Luger, P. J. Am. Chem. Soc. 1991, 113, 4218-4229.
26. Nagasawa, T.; Handa, Y.; Onogushi, Y.; Suzuki, K. Bull. Chem. Soc. Jpn. 1996, 69, 31-39.