Asymmetric homologation of ketones. A new entry to orthogonally protected (2R,4R)-piperidine-2,4-dicarboxylic acid.
A new conformationally constrained analogue of glutamic acid has been synthesized efficiently in seven steps from a chiral 2-alkyl-4-piperidone. The synthesis is based on (a) the unprecedented asymmetric one-carbon homologation of the ketone controlled by the size of the N-substituent and (b) the appropriate manipulation of substituents at positions 2 and 4 of the piperidine ring, a step that involves two independent oxidation processes.
Etayo
Pablo
P
Departamento de Química Orgánica, Instituto de Ciencia de Materiales de Aragón, Instituto Universitario de Catálisis Homogénea, Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain.
Badorrey
Ramón
R
Díaz-de-Villegas
María D
MD
Gálvez
José A
JA
D018698:Glutamic Acid / Q000031:analogs & derivatives; D007659:Ketones / Q000737:chemistry*; D008968:Molecular Conformation; D010875:Pipecolic Acids / Q000138:chemical synthesis*; D010881:Piperidones / Q000737:chemistry
D007659:Ketones; D010875:Pipecolic Acids; D010881:Piperidones; D018698:Glutamic Acid; C041091:2,4-piperidinedicarboxylic acid