%0 Journal Article
%T Synthesis of conformationally restricted glutamate and glutamine derivatives from carbonylation of orthopalladated phenylglycine derivatives
%A Esteban P. Urriolabeitia
%A Eduardo Laga
%A Carlos Cativiela
%J Beilstein Journal of Organic Chemistry
%D 2012
%I 
%R 10.3762/bjoc.8.179
%X A new method for the regioselective synthesis of 2-alkoxycarbonyl- and 2-(aminocarbonyl)phenylglycinate methyl esters has been developed. The reaction of the orthopalladated complex [Pd(¦Ì-Cl)(C6H4(CH(CO2Me)NMe2)-2)]2 (1) with nucleophiles HNu under a CO atmosphere results in the selective incorporation of the C(O)Nu moiety to the phenyl ring and formation of the carbonyl species ortho-C6H4(C(O)Nu)(CH(CO2Me)NMe2) (2a¨Cj) (Nu = OR, NHR, NR2). Compounds 2a¨Cj are conformationally restricted analogues of glutamic acid and glutamine and are interesting due to their biological and pharmacological properties. The reaction of [Pd(¦Ì-Cl)(C6H4(CH(CO2Me)NHTf)-2)]2 (3) with nucleophiles in a CO atmosphere results, however, in the formation of the cyclic isoindolinone or the open 2-carboxyphenylglycine methyl esters, with the reaction outcome being driven by the choice of the solvent.
%K C¨CH functionalization
%K carbonylation
%K glutamic acid
%K glutamide
%K palladium
%K phenylglycine
%U http://dx.doi.org/10.3762/bjoc.8.179