STRUCTURAL CONSEQUENCES OF THE ADDITION OF LITHIUM HALIDES IN ENOLIZATION AND ALDOL REACTIONS

Aggregates consisting of lithium halides with either lithium amides or lithium enolates have been characterized by X-ray crystallography. Tw o structural types, solvated heterodimers and heterotrimers, have been found for halide/amide combinations. Two compounds containing both li thium halide and lithium enolate have also been identified as heterodi mers. Using this information, we propose a reaction sequence for enoli zation and subsequent aldol addition reaction involving halide-contain ing aggregates. An nb initio and PM3 theoretical study of model system s shows that solvated heterodimers between LiBr and either LiNH2 or Li OC(H)=CH2 are favored over the respective homodimers. Calculations rev eal a stable eight-membered ring transition state for the enolization step between LiCl . LiNH2 andacetaldehyde. Two independent transition states, a 4,8 and a 4,4,6 ring system, were calculated for the model r eaction between the heterotrimer [(LiNH2)(2) . LiCl] and acetaldehyde. Dissociation of donor solvent was computed to require more energy for heterodimers than for homodimers.