The mechanism of polyleucine catalysed asymmetric epoxidation.
Catalysis in the Julia-Colonna epoxidation of alpha,beta-unsaturated ketones is due to binding of the hydroperoxide enolate intermediate by the three N-terminal amidic N-H groups of alpha-helical poly-leucine; the N-terminal pair forms an oxy-anion hole, whilst the third aids displacement of hydroxide.
Kelly
David R
DR
Department of Chemistry, Cardiff University, P. O. Box 912, Cardiff, Wales, UKCF10 3TB. KellyDR@Cardiff.ac.uk
Roberts
Stanley M
SM
D002384:Catalysis; D002599:Chalcone / Q000737:chemistry; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006860:Hydrogen Bonding; D007659:Ketones / Q000737:chemistry; D008958:Models, Molecular; D010455:Peptides / Q000737:chemistry*
D004852:Epoxy Compounds; D007659:Ketones; D010455:Peptides; C027819:polyleucine; D002599:Chalcone