Structural investigation of organic donor orbitals and their effects on reactivity in cubane, Beckmann fragmentation and seleniranium systems

Abstract

A combination of X-ray crystallographic, theoretical and mass spectrometric approaches have been used to assess the extent and affects of several stereoelectronic interactions. The donor ability of strained cubane bonds was assessed with a variable oxygen probe approach and compared to previously studied strained donor C-C bonds and an equivalent unstrained bond. The found slopes for the derivatives of the cubylmethanol and 4-methoxycarbonyl-cubylmethanol to be -2.33 x 10-3 and -2.79 x 10-3 respectively. These slopes indicated a donor ability that was similar to cyclobutyl (3.90 x 10-3 with an additional C-H donor), but lower than cyclopropyl (4...