Lithium hexamethyldisilazide (LiHMDS) in triethylamine (Et3N)/toluene is shown to enolize acyclic ketones and esters rapidly and with high E/Z selectivity. Mechanistic studies reveal a dimer-based mechanism consistent with previous studies of LiHMDS/Et3N. E/Z equilibration occurs when <2.0 equiv of LiHMDS are used. Studies of the aldol condensation and Ireland-Claisen rearrangement of the resulting Et3N-solvated enolates show higher and often complementary diastereoselectivities when compared with analogous reactions in THF. The Et3N-solvated enolates also display a marked (20-fold) acceleration of the Ireland-Claisen rearrangement with evidence of autocatalysis. A possible importance of amine-solvated enolates is discussed.