Novel cleavage of propargylamines by reaction with organolithium compounds

Journal of Organic Chemistry

Volumn 61, Issue 11, 1996, Pages 3646-3649

  Barluenga, José ^a   Canteli, Rosa María ^a   Flórez, Josefa ^a  

^a UNIVERSITY OF OVIEDO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001414444     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960025+     Document Type: Article

References (19)

1. Barluenga, J.; Canteli, R. M.; Flórez, J. J. Org. Chem. 1994, 59, 602.
2. (a) Richey, H. G., Jr.; Erickson, W. F. J. Org. Chem. 1983, 48, 4349.
3. (b) Richey, H. G., Jr.; Cabré, S. J. Org. Chem. 1983, 48, 3822.
4. Becker, K. B.; Grob, C. A. The Formation of Unsaturated Groups by Heterolytic Fragmentation. In The Chemistry of Functional Groups; Patai, S., Ed.; Wiley: London, 1977; Supp. A, p 653.
5. (a) Wiley, R. H.; Davis, R. P. J. Am. Chem. Soc. 1954, 76, 3496.
6. (b) Beecham, A. F. J. Am. Chem. Soc. 1957, 79, 3257.
7. Grob, C. A. Angew. Chem. 1969, 81, 543; Angew. Chem., Int. Ed. Engl. 1969, 8, 535.
8. Grob, C. A. Angew. Chem. 1969, 81, 543; Angew. Chem., Int. Ed. Engl. 1969, 8, 535.
9. Gladych, J. M. Z.; Hartley, D. Polyfunctional Amines. In Comprehensive Organic Chemistry; Barton, D. H. R., Ollis, W. D., Eds.; Pergamon: Oxford, 1979; Vol. 2, p 61.
10. Lee, L. Y. C.; Ci, X.; Giannotti, C.; Whitten, D. G. J. Am. Chem. Soc. 1986, 108, 175.
11. (a) Beak, P.; Meyers, A. I. Acc. Chem. Res. 1986, 19, 356.
12. 2=NBu cannot be ruled out, picture 15 could be a better model for the fragmentation reaction, given that organolithium 14 is stable at rt (does not decompose by β-elimination) in the absence of any other organolithium compound.
13. A factor which may contribute to this difference may have to do with the larger size of benzyl group compared to butyl group.
14. The partial conversion of diamine 18 to hexahydropyrimidine 19, although was observed in some cases upon silica gel column chromatography or during distillation (0.001 mmHg), seems to be a much less favored process.
15. D'Amico, J. J.; Harman, M. W.; Cooper, R. H. J. Am. Chem. Soc. 1957, 79, 5270.
16. Barluenga, J.; Olano, B.; Fustero, S. J. Org. Chem. 1985, 50, 4052.
17. Nobis, J. F.; Moormeier, L. F. Ind. Eng. Chem. 1954, 46, 539.
18. Elderfield, R. C.; Hageman, H. A. J. Org. Chem. 1949, 14, 605.
19. Bortnick, N.; Luskin, L. S.; Hurwitz, M. D.; Craig, W. E.; Exner, L. J.; Mirza, J. J. Am. Chem. Soc. 1956, 78, 4039.