Energetics of hydrate and hemiketal formation for highly fluorinated ketones

Tetrahedron Letters

Volumn 37, Issue 51, 1996, Pages 9165-9168

  Lindner, Patrick E ^a   Lemal, David M ^a  

^a Lamont Doherty Earth Observatory   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

KETONE;

ARTICLE; CHEMICAL REACTION; DRUG SYNTHESIS; ENERGY TRANSFER; HYDRATION; STEREOSPECIFICITY;

EID: 0030590994     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(96)02149-1     Document Type: Article

References (14)

1. 1. (a) Guthrie, J.P. Can. J. Chem. 1975, 53, 898.
2. (b) Rogers, F.E.; Rapiejko, R.J. J. Am. Chem. Soc. 1971, 93, 4596.
3. 2. Middleton, W.J.; Linsey, R.V. J. Am. Chem. Soc. 1964, 86, 4948.
4. 3. Knunyants, I.L.; Chen, T.Y.; Gambaryan, N.P. Izv. Akad. Nauk SSSR 1960, 686.
5. 4. Perfluorocyclobutanone, for example, forms a stable hydrate (mp 52 °C). England, D. C. J. Am. Chem. Soc. 1961, 83, 2205.
6. 5. (a) Correa, R.A.; Lindner, P.E.; Lemal, D.M. J. Am. Chem. Soc. 1994, 116, 10795.
7. (b) Lindner, P.E.; Correa, R.A.; Gino. J.; Lemal, D.M. J. Am. Chem. Soc. 1996, 118, 2556.
8. (c) Lindner, P.E.; Lemal, D.M. J. Org. Chem. 1996, 61, 5109.
9. -1 scaled by 0.893. Hehre, W.J.; Radom, L.; Schleyer, P.v.R.; Pople, J.S. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986.
10. 7. This follows the lead of Wiberg, et al. who used the same approach while examining the hydration of hydrocarbon-derived ketones. Wiberg, K.B.; Morgan, K.M.; Maltz, H. J. Am. Chem. Soc. 1994, 116, 11067.
11. hyd(298K) or pentafluoroacetone is -18.6 kcal/mol at the HF/6-31G**//6-31G** level of theory.
12. 9. For a full discussion of the enolization of ketones 1 and 2, see reference 5.
13. 10. The synthesis of ketone 5 has been reported previously (reference 5c).
14. 11. The ratio of diastereomeric ketals was 1:1 for 7 but 7:1 for 5, and only a single isomer was found for 4. Presumably the diastereomers with hydroxyl cis to bromine are favored for steric reasons. Because of signal overlap, the ratio was not determined for 6.