Palladium(II) trifluoroacetate (5 mol %) catalyzes the C-arylation of N,N-disubstituted hydantoins by aryl iodides in good yield. The reaction proceeds through base-promoted enolization of the amino acid derived hydantoins, and the resulting 5,5-disubstituted hydantoins may be deprotected at one or both N atoms to yield biologically active structures or alternatively hydrolyzed to the parent α-aryl α-amino acids. The reaction is successful with a variety of parent amino acids and a range of electron-rich and electron-poor aryl iodides.

Palladium Catalyzed C-Arylation of Amino Acid Derived Hydantoins. -Various aryl iodides are suitable reactants under conditions A) to produce the desired 5,5-disubstituted hydantoin structures. The products can be deprotected at both nitrogens [cf. phenytoin (X)] or selectively at one N-position. Alternatively, hydrolysis leads to formation of the parent amino acid [cf.(XI)]. -(FERNANDEZ-NIETO, F.; MAS ROSELLO, J.; LENOIR, S.; HARDY, S.; CLAYDEN*, J.; Org. Lett. 17 (2015) 15, 3838-3841, http://dx.doi.org/10.1021/acs.orglett.5b01803 ; Sch. Chem., Univ. Manchester, Manchester M13 9PL, UK; Eng.) -Lehmann 51-135