Inter vs. Intramolecular bridge mediated Electron Transfer to Aliphatic Halides.

URANGA, J.G; VERA, D.M.; SANTIAGO, A.N. Y PIERINI, A.B.

ACS

Lugar: EEUU; Año: 2006 vol. 71 p. 6596 - 6596

font face="Times New Roman" size="2"> 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 by either 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.