Vinylalumination of fluoro-carbonyl compounds

Tetrahedron Letters

Volumn 39, Issue 48, 1998, Pages 8791-8794

  Ramachandran, P Veeraraghavan ^a   Reddy, M Venkat Ram ^a   Rudd, Michael T ^a   De Alaniz, Javier Read ^a  

^a PURDUE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACRYLIC ACID ETHYL ESTER; ALDEHYDE; CARBONYL DERIVATIVE; FLUORINE DERIVATIVE; KETONE; VINYL DERIVATIVE;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL REACTION; CHIRALITY; COLUMN CHROMATOGRAPHY; FLUORINATION; GAS CHROMATOGRAPHY; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 0032569896     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)01974-1     Document Type: Article

References (16)

1. 1. Preliminary results were presented at the 31st Great Lakes Regional Meeting (Paper # 233) of the American Chemical Society, Milwaukee, WI, June 2, 1998.
2. 2. (a) Post-doctoral research associate on a grant from the Purdue Borane Research Fund.
3. (b) Pfizer Summer Undergraduate Research Fellow
4. (c) Purdue University Summer Undergraduate Research Fellow from Fort Lewis College, Fort Lewis, CO.
5. 3. For several recent reviews see: Biomedical Frontiers of Fluorine Chemistry, Ojima, I.; McCarthy, J. R.; Welch, J. T. Eds. ACS Symposium Series 639, American Chemical Society, Washington DC, 1996.
6. 4. Ramachandran, P. V.; Brown, H. C. in EPC-Synthesis of Fluoro-Organic Compounds, Soloshonok, V. A. Ed. Wiley: Chichester, U. K. , 1998, in press.
7. 5. For the most recent review on Baylis-Hillman reaction, see: Ciganek, E. in Organic Reactions 1997, 51, 201. Paquette, L. A. ed. John Wiley, New York, NY.
8. 6. Tsuda, T.; Yoshida, T.; Saegusa, T. J. Org. Chem. 1988, 53, 1037.
9. 7. Golubev, A. S.; Galakhov, M. V.; Kolomiets, A. F.; Fokin, A. V. Izv. Akad. Nauk Ser. Khim. 1992, 2763.
10. 8. Fluoral polymerizes instantaneously in the presence of a trialkylamine. Busfield, W. K.; Whalley, E. Polymer 1966, 7, 541.
11. 3COMe is known to polymerize in the presence of secondary amines. Dhingra, M. M.; Tatta, K. R. Org. Mag. Res. 1977, 9, 23.
12. 10. Zu, L. H.; Kundig, E. P. Helv. Chim. Acta 1994, 77, 1480.
13. 11. Génisson, Y.; Massardier, C.; Gautier-Luneau, I.; Greene, A. E. J. Chem. Soc. Perkin Trans. I 1996, 2869.
14. 12. The reaction was followed by quenching an aliquot and comparing with ethyl cinnamate using a GC. Allowing the reaction to warm to rt for 1 h achieved 80% hydroalumination, with no further improvement with time. Increasing the ratio of the DIBAL-H to propiolate to 1.8 improved the yield of the cinnamate to 90% after 1 h at rt, which was essentially complete in 1.5 h.
15. 1H NMR spectra. We believe that the reaction proceeds via an allenoate intermediate as described by Marino. Marino, J. P.; Linderman, R. J.; J. Org. Chem. 1983, 48, 4621.
16. 1 we noticed a report where the reagent 7 was utilized for similar reactions, albeit in moderate yields, with non-fluorinated substrates in presence of a Lewis acid. Li, G.; Wei, H. X.; Willis, S. Tetrahedron Lett. 1998, 39, 4607.