Solution and Solid Phase Synthesis of Unusual a-Amino Acids From

the glutamate dimer. It may also be possible to introduce psubstituted glutamate
derivatives (such as 4.73) into pre-generated mixtures of the enolate of 4.69. ensuring the
high stereochemistry is pre-instaiied.
1,4-Additions to E and Z dehydroglutarnic acids would provide access to B-
substituted glutarnic acids, of immense interest in the synthesis of kainic acid analogues
which possess potent neuroexcitatory activity? Cumnt synthetic methods used in the
synthesis of these denvatives suffer from a lack of generality in the incorporation of
various substituents andfor poor stereoselectivity. 1,2-S tereoinduction has been used
with great success in a number of Michael additions and the proximity of the OB0 ester
may ensure hi& stereoselectivity in these reactions (Scheme 7.1).
Scheme 7.1
C02Me
Epoxidation of the dehydroglutamic acids, although unsuccess€ul under
conditions reported in this thesis, warrants further investigation due to its synthetic utility.
Nucleophilic ring-opening reactions to give p-substitu ted-ph ydrox y-glutamic acids are
of interest not only as potential iGlu and mGlu agonists/antagonists but also as
intermediates in natural product syntheses due to their highly functionalized nature.
As a naturai extension of the high 19-induction of addition to protected glutarnic
acid denvatives, investigation of the potential 1,4-induction of L-a-aminoadipic acid
should be explored. Various analogs of L-a-arninoadipic acid have been incorporated in