A remarkable [2.2.2] propellane

Journal of the American Chemical Society

Volumn 125, Issue 19, 2003, Pages 5590-5591

  He, Yigang ^a   Junk, Christopher P ^a   Cawley, John J ^a   Lemal, David M ^a  

^a Dartmouth College   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANE DERIVATIVE;

ARTICLE; CHEMICAL BOND; CRYSTAL STRUCTURE; CYCLOADDITION; DEBROMINATION; DIELS ALDER REACTION; QUANTITATIVE ANALYSIS; SYNTHESIS; TEMPERATURE;

EID: 0038296973     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja030077y     Document Type: Article

References (17)

1. Walter H. Stockmayer Fellow, 1998-2000.
2. Wiberg, K. B. Chem. Rev. 1989, 89, 975. The strain energy of the parent [2.2.2]propellane was calculated to be 97 kcal/mol.
3. Eaton, P. E.; Temme, G. H. J. Am. Chem. Soc. 1973, 95, 7508.
4. Zhang, Y.; Smith. J. R.; Lemal, D. M. J. Am. Chem. Soc. 1996, 118, 9454.
5. This molecule was chosen as a model for perfluoro[2.2.2]propellane, which has not yet submitted to synthesis. Oxygen plays a duel role as substituent, greatly facilitating propellane formation by virtue of its π donor ability, then mimicking fluorine in the product with its electron-withdrawing power as the second most electronegative element.
6. This new ketene acetal was prepared by treatment of 2-trifluoromethyl-1,3-dioxolane with butyllithium.
7. +) 347.0130; found 347.0127
8. Almenningen, A.; Bastiansen, O.; Skancke, P. N. Acta Chem. Scand. 1961, 15, 711. See also: Stein, A.; Lehmann, C. W.; Luger, P. J. Am. Chem. Soc. 1992, 114, 7684.
9. Almenningen, A.; Bastiansen, O.; Skancke, P. N. Acta Chem. Scand. 1961, 15, 711. See also: Stein, A.; Lehmann, C. W.; Luger, P. J. Am. Chem. Soc. 1992, 114, 7684.
10. Despite its high degree of p character, ab initio calculations predict the central bond of the parent hydrocarbon to be only 1.51 A long: Zhao, C.-Y.; Zhang, Y.; You, X.-Z. J. Phys. Chem. A 1997, 101. 5174-5182.
11. Wiberg, K. B.; Bader, R. F. W.; Lau, C. D. H. J. Am. Chem. Soc. 1987, 109, 985.
12. Liebman, J. F.; Dolbier, W. R., Jr.; Greenberg, A. J. Phys. Chem. 1986, 90, 394.
13. Handbook of Chemistry and Physics; Lide, D. R., Ed.; 83rd ed.; CRC Press: Boca Raton, FL, 2002-2003; pp 8-22, 8-23.
14. The two bridgeheads should be coupled primarily by through-bond interaction: Stohrer, W. D.; Hoffmann, R. J. Am. Chem. Soc. 1972, 94, 779.
15. 2O both bridgeheads become deuterated.
16. 13C spectrum, it was the signal for C4 that was split into a quartet by the methyl protons.
17. Kirby, A. J. The Anomeric Effect and Related Stereoelectronic Effects at Oxygen; Springer: New York, 1983.