Birch Reductive Alkylation of Methyl <i>m</i>‑(Hydroxymethyl)benzoate Derivatives and the Behavior of <i>o</i>- and <i>p</i>‑(Hydroxymethyl)benzoates under Reductive Alkylation Conditions

Abstract

Birch reductive alkylation of methyl <i>m</i>-(hydroxymethyl)­benzoate derivatives, using lithium in ammonia–tetrahydrofuran in the presence of <i>tert</i>-butyl alcohol, can be achieved without significant loss of benzylic oxygen substituents. Similar treatment of <i>o</i>- and <i>p</i>-(hydroxymethyl)­benzoate derivatives results largely in loss of benzylic oxygen substituents. The results are rationalized by computations describing electron density patterns in the putative radical anion intermediate involved in these reactions