Birch Reductive Alkylation of Methyl m‑(Hydroxymethyl)benzoate Derivatives and the Behavior of o- and p‑(Hydroxymethyl)benzoates under Reductive Alkylation Conditions
journal contributionposted on 04.01.2013, 00:00 authored by Samuel J. Fretz, Christopher M. Hadad, David J. Hart, Shubham Vyas, Dexi Yang
Birch reductive alkylation of methyl m-(hydroxymethyl)benzoate derivatives, using lithium in ammonia–tetrahydrofuran in the presence of tert-butyl alcohol, can be achieved without significant loss of benzylic oxygen substituents. Similar treatment of o- and p-(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.