The chemo- and enantioselective cyclopropanation of polyenes: Chiral auxiliary vs chiral reagent-based approach

Tetrahedron Letters

Volumn 37, Issue 44, 1996, Pages 7925-7928

  Charette, André B ^a   Juteau, Hélène ^a   Lebel, Hélène ^a   Deschênes, Denis ^a  

^a UNIVERSITÉ DE MONTRÉAL   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPROPANE DERIVATIVE;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; ENZYME ACTIVITY; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY; TECHNIQUE;

EID: 0030605056     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01798-4     Document Type: Article

References (18)

1. 1. (a) Charette, A. B.; Juteau, H. J. Am. Chem. Soc. 1994, 116, 2651-2652.
2. (b) Charette, A. B.; Prescott, S.; Brochu, C. J. Org. Chem. 1995, 60, 1081-1083.
3. 2. Simmons, H. E.; Cairns, T. L.; Vladuchick, S. A.; Hoiness, C. M. Org. React. 1973, 20, 1-131.
4. 3. Molander, G. A.; Harring, L. S. J. Org. Chem. 1989, 54, 3525-3532.
5. 4. Regioselective cyclopropanation of allenic alcohols, see: Lautens, M.; Delanghe, P. H. M. J. Am. Chem. Soc. 1994, 116, 8526-8535.
6. 5. (a) Furukawa, J.; Kawabata, N.; Nishimura, J. Tetrahedron 1968, 24, 53-58.
7. (b) Furukawa, J.; Kawabata, N.; Fujita, T. Tetrahedron 1970, 26, 243-250.
8. 2Zn in toluene at 0 °C resulted in the formation of the monocyclopropane with excellent chemoselectivity (≥95%) and yield (>95%).
9. 7. For the effect of high pressure of the chemoselectivity see: Guerreiro, M. C.; Schuchardt, U. Synth. Commun. 1996, 26, 1793-1800.
10. 8. During the course of our study, a first example of a selective cyclopropanation of a polyene was reported using the dioxaborolane 1: Barrett, A. G. M.; Kasdorf, K. J. C. S., Chem. Comm. 1996, 325-326.
11. 2 without DME led to irreproducible results.
12. 10. The 2,4-dienols in entry 1-3 were prepared from the corresponding aldehyde by a standard Horner-Emmons/reduction sequence. For the synthesis of the starting aldehyde in entry 2 and 3, see: Charette, A. B.; Lebel, H. J. Am. Chem. Soc. submitted for publication.
13. 3 reduction (85%).
14. 12. Yoshida, M.; Ezaki, M.; Hashimoto, M. Yamashita, M.; Shigematsu, N.; Okuhara, M.; Kohsaka, M.; Horikoshi, K. J. Antibiotics 1990, 43, 748-754.
15. 13. Kuo, M. S.; Zielinski, R. J.; Cialdella, J. I.; Marschke, C. K.; Dupuis, M. J.; Li, G. P.; Kloosterman, D. A.; Spilman, C. H.; Marshall, V. P. J. Am. Chem. Soc. 1995, 117, 10629-10634.
16. 14. McMurray, J. E.; Dushin, R. G. J. Am. Chem. Soc. 1990, 112, 6942-6949.
17. 2I led to a 1:1 mixture of diastereomers indicating that the remote chiral center has little effect on the stereochemical outcome of the reaction. The dioxaborolane-mediated cyclopropanation of allylic alcohols having a β-substituent have produced the corresponding cyclopropanes with slightly lower enantiomeric excesses and lower reaction rates.
18. 16. Charette, A.B.; Côté, B. J. Am. Chem. Soc. 1995, 117, 12721-12732.