Uranga Jorge G, Vera D Mariano A, Santiago Ana N, Pierini Adriana B
INFIQC - Departamento de Química Organica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5000 Córdoba, Argentina.
J Org Chem. 2006 Aug 18;71(17):6596-9. doi: 10.1021/jo060054c.
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[7.3.1.0(2,7)]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/C-Cl 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.
利用密度泛函理论（DFT）方法并在溶液中进行完全几何优化，对1-氯双环[2.2.1]庚-2-酮、4-氯双环[2.2.1]庚-2-酮、1-氯双环[2.2.2]辛-2-酮、4-氯双环[2.2.2]辛-2-酮、1-氯金刚烷-2-酮、5-氯金刚烷-2-酮以及2-氯三环[7.3.1.0(2,7)]十三烷-13-酮的阴离子表面进行了研究。这些化合物的还原裂解受多环的刚性、形成无张力自由基的能力以及桥上羰基/C-Cl的相对位置控制。这种控制可以通过以自由基阴离子为中间体的协同解离或逐步机制来实现。5-氯金刚烷-2-酮是遵循后一种途径的最合适化合物。
