A synthetically useful source of propargyl radicals

Tetrahedron Letters

Volumn 37, Issue 31, 1996, Pages 5495-5498

  Denieul, Marie Pierre ^a   Quiclet Sire, Béatrice ^a   Zard, Samir Z ^a,b  

^a CNRS   (France)

^b LABORATOIRE DE SYNTHÈSE ORGANIQUE   (France)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; TECHNIQUE;

EID: 0030605834     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01146-X     Document Type: Article

References (22)

1. 1. (a) Curran, D. P. in Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I., Eds; Pergamon Press: Oxford, 1991; Vol. 4, pp 715-831.
2. (b) Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon Press: Oxford, 1986.
3. (c) Motherwell, W. B.; Crich, D. Free Radical Chain Reactions in Organic Synthesis; Academic Press: London, 1991.
4. 2. (a) Pasto, D. J.; Krasnansky, R.; Zercher, C. J. Org. Chem. 1987, 52, 3062-3072.
5. (b) Luedtke, A.; Meng, K.; Timberlake, J. W. Tetrahedron Lett. 1987, 28, 24255-4258.
6. 3. See for example: (a) Hudrlik, P. F.; Hudrlik, A. M. in The Chemistry of the Carbon-Carbon Triple Bond; Patai, S., Ed.; John Wiley & Sons: Chichester, 1978; chap. 7, pp 199-273.
7. (b) Corey, E. J.; Cheng, X.-M. The Logic of Chemical Synthesis; J. Wiley & Sons: New York, 1989; many of the total syntheses discussed by Corey and Cheng involve acetylene chemistry.
8. 4. a) Delduc, P.; Tailhan, C.; Zard, S. Z. J. Chem. Soc., Chem. Comm. 1988, 308-310.
9. b) Mestre, F.; Tailhan, C. ; Zard, S. Z. Heterocycles 1989, 28 , 171-174.
10. c) Forbes, J. E. ; Zard, S. Z. Tetrahedron Letters, 1989, 30, 4367-4370.
11. d) J. E. Forbes; S. Z. Zard, J. Am. Chem. Soc. 1990, 112, 2034-2035.
12. e) Forbes, J. E.; Tailhan, C.; Zard, S. Z. Tetrahedron Lett. 1990, 31, 2565-2568.
13. f) Boivin, J.; Camara, J.; Zard, S. Z. J. Am. Chem. Soc. 1992, 114, 7909-7910.
14. g) Forbes, J. E.; Zard, S. Z. Tetrahedron 1993, 49, 8257-8268.
15. h) Axon, J.; Boiteau, L.; Boivin, J.; Forbes, J. E.; Zard, S. Z. Tetrahedron Lett. 1994, 35, 1719-1722.
16. i) For a short review, see: Zard, S. Z. Actualité Chim. 1993, (3), 10-14.
17. 5. Boivin, J.; Tailhan, C.; Zard, S. Z. J. Am. Chem. Soc. 1991, 113, 5874-5876.
18. 6. The radical chain path for formation of allene 5 can be pictured as follows: (equation presented)
19. 7. Boivin, J.; Tailhan, C.; Zard, S. Z. Tetrahedron Lett. 1992, 33, 7853-7856.
20. 8. Following our initial work on S-propargyl xanthates (ref. 5), one report appeared concerning the formation of an allene by cyclisation of a propargyl radical generated using tributylstannane: F.-H. Wartenberg; H. Junga; Blechert, S. Tetrahedron Lett. 1993, 34, 5251-4252. For another very recent example using sulfone chemistry, see: Quiclet-Sire, B.; Zard, S. Z. J. Am. Chem. Soc. 1996, 118, 1209-1210.
21. 8. Following our initial work on S-propargyl xanthates (ref. 5), one report appeared concerning the formation of an allene by cyclisation of a propargyl radical generated using tributylstannane: F.-H. Wartenberg; H. Junga; Blechert, S. Tetrahedron Lett. 1993, 34, 5251-4252. For another very recent example using sulfone chemistry, see: Quiclet-Sire, B.; Zard, S. Z. J. Am. Chem. Soc. 1996, 118, 1209-1210.
22. 9. Typical experimental procedure: A solution of the xanthate (2 mmoles) and olefinic trap (1 mmol) in degassed cyclohexane (4 ml) is heated to reflux under argon with periodical addition od dilauroyl peroxide (2% every 1.5-2 hrs) until consumption of the starting material. The solvent is distilled off under reduced pressure, and the residue purified by column chromatography on silica gel.