Inter- and Intramolecular-Bridge-Mediated Electron Transfer in Aliphatic Halides

J. G. URANGA; D. M. A. VERA; A.S. SANTIAGO; A. B. PIERINI

JOURNAL OF ORGANIC CHEMISTRY

American Chemical Society

Lugar: New York; Año: 2006 vol. 72 p. 6596 - 6599

0022-3263

The anionic surfaces of the 1-chloro- and 4-chlorobicyclo-[2.2.1]heptan-2-one, 1-chloro- and 4-chlorobicyclo[2.2.2]-octan-2-one, 1-chloro- and 5-chloroadamantan-2-one, and 2-chlorotricyclo[7.3.1.02,7]tridecan-13-one were explored using DFT functionals with full geometry optimization in solution. The reductive cleavage of these compounds is controlled by the rigidity of the polycycle, its capability to form an unstrained radical, and by the relative carbonyl/CCl disposition on the bridge. Such control can be exerted byeither a concerted-dissociative or a stepwise mechanism with radical anions as intermediates. 5-Chloroadamantan-2-one is the most suitable compound to follow the latter pathway.