Unprecedented C-6 functionalisation of 3-picoline induced by a methyl to C-6 lithium shift

Chemical Communications

Volumn , Issue 11, 2000, Pages 951-952

  Mathieu, Julien ^a   Gros, Philippe ^a   Fort, Yves ^a  

^a NANCY UNIVERSITÉ   (France)

Author keywords

[No Author keywords available]

Indexed keywords

LITHIUM; METHYL GROUP; PICOLINE DERIVATIVE; PYRIDINE DERIVATIVE;

AROMATIZATION; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL MODIFICATION; CHEMICAL REACTION; COMPLEX FORMATION; REACTION ANALYSIS;

EID: 0034616856     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/b001690j     Document Type: Article

References (15)

1. M. L. Davis, B. J. Wakefield and J. A Wadell, Tetrahedron, 1992, 5, 939; W. M. Stalick and J. H. Murray, Org. Prep. Proced. Int., 1994, 26, 677.
2. M. L. Davis, B. J. Wakefield and J. A Wadell, Tetrahedron, 1992, 5, 939; W. M. Stalick and J. H. Murray, Org. Prep. Proced. Int., 1994, 26, 677.
3. F. Effenberger, A. Krebs and P. Willrett, Chem. Ber., 1992, 125, 1131; G. A. Kraus and J. Malpert, Synlett, 1997, 1, 107; G. Hanan, U. Schubert, D. Volkmer, E. Rivière, J.-M. Lehn, N. Kyritsakas and J. Fisher, Can. J. Chem., 1997, 75, 169.
4. F. Effenberger, A. Krebs and P. Willrett, Chem. Ber., 1992, 125, 1131; G. A. Kraus and J. Malpert, Synlett, 1997, 1, 107; G. Hanan, U. Schubert, D. Volkmer, E. Rivière, J.-M. Lehn, N. Kyritsakas and J. Fisher, Can. J. Chem., 1997, 75, 169.
5. F. Effenberger, A. Krebs and P. Willrett, Chem. Ber., 1992, 125, 1131; G. A. Kraus and J. Malpert, Synlett, 1997, 1, 107; G. Hanan, U. Schubert, D. Volkmer, E. Rivière, J.-M. Lehn, N. Kyritsakas and J. Fisher, Can. J. Chem., 1997, 75, 169.
6. Ph. Gros, Y. Fort and P. Caubère, J. Chem. Soc., Perkin Trans. 1, 1997, 20, 3071; Ph. Gros, Y. Fort and P. Caubère, J. Chem. Soc., Perkin Trans. 1, 1997, 24, 3597; Ph. Gros, C. Ben Younès-Millot and Y. Fort, Tetrahedron Lett., 2000, 41, 303; S. Choppin, Ph. Gros and Y. Fort, Org. Lett., 2000, in press.
7. Ph. Gros, Y. Fort and P. Caubère, J. Chem. Soc., Perkin Trans. 1, 1997, 20, 3071; Ph. Gros, Y. Fort and P. Caubère, J. Chem. Soc., Perkin Trans. 1, 1997, 24, 3597; Ph. Gros, C. Ben Younès-Millot and Y. Fort, Tetrahedron Lett., 2000, 41, 303; S. Choppin, Ph. Gros and Y. Fort, Org. Lett., 2000, in press.
8. Ph. Gros, Y. Fort and P. Caubère, J. Chem. Soc., Perkin Trans. 1, 1997, 20, 3071; Ph. Gros, Y. Fort and P. Caubère, J. Chem. Soc., Perkin Trans. 1, 1997, 24, 3597; Ph. Gros, C. Ben Younès-Millot and Y. Fort, Tetrahedron Lett., 2000, 41, 303; S. Choppin, Ph. Gros and Y. Fort, Org. Lett., 2000, in press.
9. Ph. Gros, Y. Fort and P. Caubère, J. Chem. Soc., Perkin Trans. 1, 1997, 20, 3071; Ph. Gros, Y. Fort and P. Caubère, J. Chem. Soc., Perkin Trans. 1, 1997, 24, 3597; Ph. Gros, C. Ben Younès-Millot and Y. Fort, Tetrahedron Lett., 2000, 41, 303; S. Choppin, Ph. Gros and Y. Fort, Org. Lett., 2000, in press.
10. The reaction with 2 equiv. of BuLi-LiDMAE led also to clean C-6 substitution but in lower yield (76%).
11. Condensation with epoxides (styrene oxide and propylene oxide) was also attempted but was found to be unsuccessful and 3-picoline was recovered quantitatively in both cases.
12. R. Fraser, T. Mansour and S. Savard, J. Org. Chem., 1985, 50, 3232.
13. Examples using KIE to control the regioselectivity of lithiations have been reported. See, for example: M. Kopach and A. I. Meyers, J. Org. Chem., 1996, 61, 6764; J. Clayden, J. Pink, N. Westlund and F. Wilson, Tetrahedron Lett., 1998, 39, 303.
14. Examples using KIE to control the regioselectivity of lithiations have been reported. See, for example: M. Kopach and A. I. Meyers, J. Org. Chem., 1996, 61, 6764; J. Clayden, J. Pink, N. Westlund and F. Wilson, Tetrahedron Lett., 1998, 39, 303.
15. Despite all our efforts we were unable to isolate the hydro intermediate.