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Pure Appl. Chem., 2003, Vol. 75, No. 5, pp. 549-562

New structurally interesting cyclopropane derivatives. A world of wonders and surprises

A. de Meijere1*, S. I. Kozhushkov1, A. A. Fokin2, I. Emme1, S. Redlich1 and P. R. Schreiner2

1 Institut für Organische Chemie der Georg-August-Universtität Göttingen, Tammannstrasse 2,D-37077 Göttingen, Germany
2 Institut für Organische Chemie, Justus-Liebig-Universität Giessen, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany

Abstract: The structurally intriguing [4]- and [5]triangulanes have been prepared in enantiomerically pure form. Their surprisingly high specific rotations are well reproduced by DFT/SCI computations and stem from the fact that these hydrocarbons essentially are σ-helicenes (i.e., rigidly held helical arrangements of σ-bonds). Some light is shed on the properties of radical cations derived from [3]- and [4]rotanes. While the former adopts Cs or C2v symmetry, the latter retains the D4h symmetry of the neutral hydrocarbon, according to highlevel computations. Experimental and computational evidence is also presented that the antiaromatic cyclopentadienyl cation is stabilized as a singlet ground state by five cyclopropyl substituents. Yet, the three cyclopropyl groups in tricyclopropylamine do not favor the formation of its radical cation, because they are not in the proper orientation. When this amine radical cation is generated by cobalt γ-irradiation in a Freon matrix, evidence for a significant conformational change is obtained by EPR spectroscopy. Finally, the conformational dynamics of the newly prepared crowded molecules tetracyclopropyl- and tetraisopropylmethane are discussed.