Magnesium mediated carbometallation of propargyl alcohols: Direct routes to dihydroxydienes and enediyne alcohols

Tetrahedron Letters

Volumn 41, Issue 1, 2000, Pages 11-15

  Forgione, Pat ^a   Fallis, Alex G ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

Author keywords

Diene; Diol; Enediyne; Magnesium; Propargyl

Indexed keywords

ALCOHOL DERIVATIVE; ALKADIENE; ALKYNE DERIVATIVE; MAGNESIUM; ORGANOMETALLIC COMPOUND;

ARTICLE; CATALYST; CHELATION; DRUG SYNTHESIS;

EID: 0033992346     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01994-2     Document Type: Article

References (36)

1. (a) Fallis, A. G. Acc. Chem. Res. 1999, 32, 464.
2. (b) ibid. Can. J. Chem. 1999, 77, 159.
3. (c) ibid. Pure Appl. Chem. 1997, 69, 495.
4. (a) Wong, T.; Romero, M. A.; Fallis, A. G. J. Org. Chem. 1994, 59, 5527.
5. (b) Wong, T.; Tjepkema, M. W.; Audrain, H.; Wilson, P. D.; Fallis, A. G. Tetrahedron Lett. 1996, 37, 755.
6. (a) Eisch, J. J.; Husk, G. J. J. Am. Chem. Soc. 1965, 87, 4194.
7. (b) Chérest, M.; Felkin, H.; Frajerman, C.; Lion, C.; Roussi, G.; Swierczewski, G. Tetrahedron Lett. 1966, 875.
8. (c) Felkin, H.; Swierczewski, G.; Tambuté, A. Tetrahedron Lett. 1969, 707.
9. (d) Felkin, H.; Kaeseberg, C. Tetrahedron Lett. 1970, 4587.
10. (e) Eisch, J. J.; Merkley, J. H.; Galle. J. E. J. Org. Chem. 1979, 44, 587.
11. (f) Eisch, J. J.; Merkley, J. H. J. Am. Chem. Soc. 1979, 101, 1148.
12. (a) Eisch, J. J.; Merkley, J. H. J. Organomet. Chem. 1969, 20, 27.
13. (b) Richey Jr., H. G.; Von Rein, F. W. J. Organomet. Chem. 1969, 20, 32.
14. (c) Von Rein, F. W.; Richey Jr., H. G. Tetrahedron Lett. 1971, 3777.
15. (d) Labaundinière, L.; Hanaizi, J.; Normant, J.-F. J. Org. Chem. 1992, 57, 6903.
16. (e) Creton, I.; Marek, I.; Normant, J.-F. Tetrahedron Lett. 1995, 36, 7451.
17. (a) Jousseaume, B.; Duboudin, J.-G. J. Organomet. Chem. 1975, 91, C1.
18. (b) Duboudin, J. G.; Jousseaume, B. J. Organomet. Chem. 1979, 168, 1.
19. (c) Duboudin, J. G.; Jousseaume, B.; Bonakdar, A. J. Organomet. Chem. 1979, 168, 227.
20. (d) Negishi, E.; Zhang, Y.; Cederbaum, F. E.; Webb, M. B. J. Org. Chem. 1986, 51, 4080.
21. Ma, S.; Negishi, E. J. Org. Chem. 1997, 62, 784.
22. Tjepkema, M. W.; Wong, T.; Wilson, P. D.; Fallis, A. G. Can. J. Chem. 1997, 75, 1542.
23. The quality of the vinyl magnesium chloride used in these experiments is important. In our experience the Fluka product is the most reliable. Yields are reduced significantly if vinyl magnesium bromide is employed but if magnesium chloride is added this provides an alternative procedure, although the yields are reduced.
24. (a) Enediyne Antibiotics as Antitumor Agents; Borders, D. B.; Doyle, T. W., Eds.; Marcel Dekker Inc: New York, 1995.
25. (b) Nicolaou, K. C.; Smith, A. L. In Modern Acetylene Chemistry; Stang, P. J.; Diederich, F., Eds.; VCH: Weinheim, 1995; Chapter 7, pp. 203-279.
26. (c) Lhermitte, H.; Grierson, D. S. Contemp. Org. Syn. 1996, 3, 41.
27. (d) Lhermitte, H.; Grierson, D. S. Contemp. Org. Syn. 1996, 3, 43.
28. (e) Danishefsky, S. J.; Shair, M. D. J. Org. Chem. 1996, 61, 16.
29. (a) Lu, Y.-F.; Harwig, C. W.; Fallis, A. G. J. Org. Chem. 1993, 58, 4202.
30. (b) Lu, Y.-F.; Harwig, C. W.; Fallis, A. G. Can. J. Chem. 1995, 73, 2253.
31. (c) Harwig, C. W.; Py, S.; Fallis, A. G. J. Org. Chem. 1997, 62, 7902.
32. (d) Py, S.; Harwig, C. W.; Banerjee, S.; Brown, D. L.; Fallis, A. G. Tetrahedron Lett. 1998, 39, 6139.
33. Meyers, A. G.; Harrington, P. M.; Kuo, E. Y. J. Am. Chem. Soc. 1991, 113, 694.
34. Marshall, J. A.; DeHoff, B. S. J. Org. Chem. 1986, 51, 863.
35. Negishi, E.; Choueiry, D. In Preparation of Alkenes; A Practical Approach; Williams, J. M. J., Ed. Reaction of Alkynes with Organometallic Reagents. Oxford University Press: Oxford, 1996; Chapter 7, p. 152.
36. 2: C, 76.44; H, 7.90. Found: C, 76.55; H, 8.13.