Quaternary amino acids are biologically important and useful building blocks for natural product and pharmaceutical targets. However, a-arylation of amino acids is challenging with only a small number of methods available.The rearrangement chemistry established in the Clayden group has allowed us to develop a transition metal�free arylation of amino acid enolates. This works by intramolecular delivery of an aromatic ring tethered via a urea linkage and has been used to synthesise a variety of hydantoins, which are derivatives of quaternary amino acids. Investigation of the reaction mechanism using in situ infra-red spectroscopy revealed a total of six successive species on the reaction pathway.This methodology has also been extended to the challenging asymmetric synthesis of quaternary amino acids. Introduction of a chiral auxiliary to control the stereochemistry of the arylation leads to enantiomerically enriched hydantoins. Ongoing studies are aimed at developing this asymmetric methodology and converting the hydantoins formed into synthetically valuable enantiomerically enriched quaternary amino acids.

a-Arylation of amino acid enolates

248th National Meeting (2014)

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