Synthesis of ketones with alkyl phosphonates and nitriles as acyl cation equivalent: Application of dephosphonylation reaction of β-functionalized phosphonate with hydride

Synthetic Communications

Volumn 27, Issue 19, 1997, Pages 3333-3339

  Jang, Won Bum ^a   Shin, Won Suk ^a   Hong, Jong Eun ^a   Lee, Shi Yong ^a   Oh, Dong Young ^a  

^a Korea Advanced Institute of Science and Technology (KAIST)   (South Korea)

Author keywords

[No Author keywords available]

Indexed keywords

KETONE;

ARTICLE; DRUG SYNTHESIS; IN VITRO STUDY; METHODOLOGY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS;

EID: 0030753369     PISSN: 00397911     EISSN: None     Source Type: Journal    
DOI: 10.1080/00397919708005633     Document Type: Article

References (14)

1. (a) Carmeron, G. G; Milton, A. J. S. J. Chem. Soc. Perkin Trans. II, 1976, 378.
2. (b) Kharasch, M. S. And Reinmuth, O. Grignard reagents of Non-metallic Substances; Constable; London, 1954.
3. (c) Hauser C. R.; Humphlett, W. J. J. Org. Chem., 1950, 13, 359.
4. (d) Sumrell, G. J. Org. Chem., 1954, 19, 817.
5. To tell between "dephosphorylation" and "dephosphonylation", we use the term "dephosphonylation" as a limited meaning of P-C bond cleavage in compound including phosphonate group.
6. Hong, J. E; Shin, W. S.; Jang W. B.; Oh, D. Y. J. Org. Chem.,1996, 61, 2199.
7. (a) Lee, K.; Oh, D. Y. Bull. Korean Chem. Soc., 1989, 10, 613.
8. (b) Lee, K.; Oh, D. Y. Synthesis, 1991, 213.
9. (c) Lee, K.; Shin, W. S.; Oh, D. Y. Synthetic Commun., 1991, 21, 1657.
10. (d) Lee, K.; Oh, D. Y. Bull. Kor. Chem. Soc., 1991, 12, 254.
11. (e) Shin, W. S.; Lee, K.; Oh, D. Y. Tetrahedron Lett., 1995, 36, 281.
12. In general, the addition of organolithium compounds to aliphatic nitriles are subjected to various side reactions, notably α-deprotonation (ref. 1(d)). We investigated the result on that, and described that in previous report (ref. 4(b)).
13. Robinson G. E.; Vernon, J. M. J. Chem. Soc. Perkin Trans. I, 1972, 1277.
14. 4 and deuterized acid, the reaction gave the ketone 7 involving two deuteriums. Because ketones do not exchange its α-proton rapidly, this two result can be the evidence that hydride attacked the phosphorus atom directly. However in the case of enamine, proton exchange is occured rapidly in hydrolysis step, so above experiment cannot be adapted in this paper. But mechanisms of these two reactions are presumed to be identical. (Equation Presented)