Partial Reduction of Electron-deficient Pyridines

Organic Letters

Volumn 2, Issue 24, 2000, Pages 3861-3863

  Donohoe, Timothy J ^a   McRiner, Andrew J ^a   Sheldrake, Peter ^b  

^a UNIVERSITY OF MANCHESTER   (United Kingdom)

^b GLAXOSMITHKLINE   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000440720     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0065930     Document Type: Article

References (21)

1. For a general review of the partial reduction of pyridines, see: Keay, J. G. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: 1991; Vol. 8, p 579.
2. (a) Carelli, V.; Liberatore, F.; Scipione, L.; Musio, R.; Sciacovelli, O. Tetrahedron Lett. 2000, 41, 1235.
3. (b) Comins, D.; Abdullah, A. H. J. Org. Chem. 1984, 49, 3392.
4. (c) Yamada, S.-I.; Kuramoto, M.; Kikugawa, Y. Tetrahedron Lett. 1969, 3101.
5. For examples, see: (a) Sundberg, R. J.; Hamilton, G.; Trindle, C. J. Org. Chem. 1986, 51, 3672.
6. (b) Booker, E.; Eisner, U. J. Chem. Soc., Perkin Trans. 1 1975, 929.
7. (c) Fowler, F. W. J. Org. Chem. 1972, 37, 1321.
8. (a) Birch, A. J.; Karakhamor, E. A. J. Chem. Soc., Chem. Commun. 1975, 480.
9. (b) Olah, G. A.; Hunadi R. J. J. Org. Chem. 1981, 46, 715.
10. (a) Danishefsky, S.; Cavanaugh, R. J. Am. Chem. Soc. 1968, 90, 520.
11. (b) Danishefsky, S.; Cain P. Nagel, A. J. Am. Chem. Soc. 1975, 97, 380.
12. (c) Danishefsky, S.; Cain, P. J. Org. Chem. 1975, 40, 3606.
13. (d) Danishefsky, S.; Cain, P. J. Steroid Biochem. 1975, 6, 177. See also: Shaw, B. D. J. Chem. Soc. 1937, 300.
14. (d) Danishefsky, S.; Cain, P. J. Steroid Biochem. 1975, 6, 177. See also: Shaw, B. D. J. Chem. Soc. 1937, 300.
15. See: (a) Donohoe, T. J.; Ace, K. W.; Guyo, P. M.; Helliwell M.; McKenna, J. Tetrahedron Lett. 2000, 41, 989.
16. (b) Donohoe, T. J.; Guillermin, J.-B.; Frampton, C.; Walter, D. S. Chem. Commun. 2000, 465 and references therein.
17. 3 at -78 °C and treated with MeI gave no reaction; this showed that compound 3 was not formed by the addition of MeI to unreduced starting material 1 after a Birch reaction.
18. 4), and concentrated in vacuo to yield a yellow oil (0.966 g). Gradient column chromatography on silica eluting with 5:95 acetone/hexanes followed by 10:90 acetone/hexanes isolated the title compound as a pale yellow oil (0.843 g, 99%). We prefer to store these products in the freezer.
19. 4Cl solution (5 mL), on which the reaction turned light yellow/orange with a white precipitate. The reaction was allowed to warm to room temperature and then absorbed on silica. Column chromatography (with reaction dry-loaded) on silica eluting with neat hexanes (to remove the naphthalene) followed by 5:95 acetone/hexanes furnished the title compound as a yellow oil (0.381 g, 96%).
20. For an example of a stable dianion formed from reduction of a pyrrole, see: Donohoe, T. J.; Harji, R. R.; Cousins, R. P. C. Tetrahedron Lett. 2000, 41, 1327. (11) Flooding dianion C with excess methyl iodide gave two compounds (93% combined yield) each with a methyl at C-2 and the second methyl either on nitrogen or on C-5.
21. Grehn, L.; Ragnarsson, U. Angew. Chem., Int. Ed. Engl. 1984, 23, 296.