Solvent and Temperature Effects on the Reduction and Amination Reactions of Electrophiles by Lithium Dialkylaminoborohydrides

The influence of temperature and solvent effects on the reduction and amination mechanisms of iodomethane by lithium N,N-diisopropylaminoborohydride (iPr-LAB) was examined in varying concentrations of THF and dioxane. The reactions of benzyl chloride and trimethylsilyl chloride with iPr-LAB in THF were also studied. The amination of iodomethane is favored over reduction at low and room temperatures in pure THF and with increasing the amount of dioxane in THF. At higher temperatures, the reduction reaction appears to compete with the amination. In dioxane solvent, however, iodomethane yields exclusively the amination product regardless of temperature. On the other hand, reduction by iPr-LAB to the aminoborane is the only product observed in THF when benzyl chloride and trimethylsilyl chloride are used. To understand the solvent effects on the product distribution, ab initio and density functional theory (DFT) calculations were used to examine the mechanisms of reduction and amination of chloromethane and bromomethane by lithium dimethylaminoborohydride (LAB) in THF and dioxane. The results of these calculations show that the relative reaction barrier heights are significantly affected by the nature of the coordinated solvent molecule and thus lend support to the experimental observations.