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

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journal contribution
posted 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.