Perfluoroaryltetrahedranes: Tetrahedranes with extended σ-π conjugation

Journal of the American Chemical Society

Volumn 131, Issue 9, 2009, Pages 3172-3173

  Nakamoto, Masaaki ^a   Inagaki, Yusuke ^a   Nishina, Motoaki ^a   Sekiguchi, Akira ^a  

^a UNIVERSITY OF TSUKUBA   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BATHOCHROMIC SHIFT; BENZENE RING; ELECTRON-WITHDRAWING SUBSTITUENTS; ETHYNYL; HEXAFLUOROBENZENE; PENTAFLUOROPHENYL; TETRAHEDRANES; THERMALLY STABLE; TRIMETHYLSILYL; UV-VIS ABSORPTION SPECTRA;

ULTRAVIOLET SPECTROSCOPY;

BENZENE;

HEXAFLUOROBENZENE; ORGANOFLUORINE DERIVATIVE; PERFLUOROARYLTETRAHEDRANE DERIVATIVE; TETRAHYDROFURAN; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BOND; CHEMICAL STRUCTURE; CONJUGATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS; THERMODYNAMICS;

EID: 70350103567     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja810055w     Document Type: Article

References (20)

1. For reviews on tetrahedrane, see: (a) Maier, G. Angew. Chem., Int. Ed. Engl. 1988, 27, 309.
2. (b) Maier, G. Pure Awl. Chem. 1991, 63, 275.
3. (c) Lee, V. Ya.; Sekiguchi, A. In Strained Hydrocarbons; Dodziuk, H., Ed.; Wiley-VCH: Weinheim, Germany, 2009; Chapter 2.
4. (a) Maier, G.; Pfriem, S.; Schäfer, U.; Matusch, R. Angew. Chem., Int. Ed. Engl. 1978, 17, 520.
5. (b) Maier, G.; Pfriem, S.; Schäfer, U.; Malsch, K.-D.; Matusch, R. Chem. Ber. 1981, 114, 3965.
6. Maier, G.; Nuedert, J.; Wolf, O.; Pappusch, D.; Sekiguchi, A.; Tanaka, M.; Matsuo, T. J. Am. Chem. Soc. 2002, 124, 13819.
7. (a) Maier, G.; Neudert, J.; Wolf, O. Angew. Chem., Int. Ed. 2001, 40, 1674.
8. (b) Sekiguchi, A.; Tanaka, M.; Matsuo, T.; Watanabe, H. Angew. Chem., Int. Ed. 2001, 40, 1675.
9. For recent reviews of silyl-substituted cyclobutadienes, see: (a) Matsuo, T.; Sekiguchi, A. Bull. Chem. Soc. Jpn. 2004, 77, 211.
10. (b) Sekiguchi, A.; Matsuo, T. Synlett 2006, 2683.
11. Sekiguchi, A.; Tanaka, M. J. Am. Chem. Soc. 2003, 125, 12684.
12. Tanaka, M.; Sekiguchi, A. Angew Chem., Int. Ed. 2005, 44, 5821.
13. (a) Mo, Y. Org. Lett. 2006, 8, 535.
14. (b) Nemirowski, A.; Reisenauer, H. P.; Schreiner, P. R. Chem.-Eur. J. 2006, 12, 7411.
15. For experimental procedures and spectral data for 4-6 and crystal data for 4 and 6, see the Supporting Information.
16. Brooke, G. M. J. Organomet. Chem. 1977, 86, 1.
17. Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen, A. G.; Taylor, R. J. Chem. Soc., Perkin Trans. 2 1987, S1.
18. Heilbronner, E.; Jones, T. B.; Krebs, A.; Maier, G.; Malsch, K.-D.; Pocklington, J.; Schmelzer, A. J. Am. Chem. Soc. 1980, 102, 564.
19. One of the edges (the C1-C3 bond) of the tetrahedrane skeleton in 4 is perpendicular to the benzene ring: the dihedral angles C15-C14-C1-C3 and C19-C14-C1-C3 are 89.4 (3) and-91.6 (3) °, respectively. On the other hand, one of the edges of the tetrahedrane skeleton in 6 was found to be almost coplanar to the benzene ring: the dihedral angles C15-C14-C1-C4 and C19-C14-C1-C4 are 173.5 (4) and-6.8 (2) °, respectively. DFT calculations of the barrier for rotation about the C1-C14 single bond in 4 at the B3LYP/6-31G (d) level indicated that the energy difference of the two conformers is very small (0.75 kcal/mol). The slightly less favorable perpendicular structure in 4 found from the X-ray analysis (see Figure 1) may be due to crystal-packing forces.
20. Saik, V. O.; Lipsky, S. J. Phys. Chem. A 2001, 105, 10107.