Abstract
Birch reductions employing lithium metal have been performed mostly under argon due to concerns about forming metal nitrides from the reduction of dinitrogen if performed under nitrogen. Although it is generally understood that inert atmospheres are standard for Birch and Birch-type (lithium, ethylenediamine, t-BuOH, THF) reductions, the atmosphere effect on Birch reduction has not been studied. Herein, we report the reduction of model substrates using lithium metal and ethylenediamine in THF under various atmospheric conditions. The reductions under argon and nitrogen atmospheres afforded essentially the same yields. Surprisingly, oxygen not only perturbed the yields in some cases but also controlled regioselectivity for a subset of naphthalenes. We propose a mechanism underlying the unexpected oxygen-dependent regioselectivity for the Birch-type reduction of naphthalenes. This work shows that the Birch-type reduction may be performed under a nitrogen atmosphere and may account for a fraction of oxygen-sensitive Birch-type reductions.