jo047897t_si_001.pdf (9.86 MB)
Hydroxylamines as Oxygen Atom Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution
journal contribution
posted on 2005-03-18, 00:00 authored by Hideto Miyabe, Kazumasa Yoshida, Masashige Yamauchi, Yoshiji TakemotoThe viability of hydroxylamines as nucleophiles in transition-metal-catalyzed allylic substitutions
was examined. We have found that the oxygen atom of hydroxylamines having an N-electron-withdrawing substituent (also known as hydroxamic acids) acts as a reactive nucleophile. The
palladium-catalyzed O-allylic substitution of hydroxylamines with allylic carbonate afforded the
linear hydroxylamines. The selective formation of the branched hydroxylamines was observed in
iridium-catalyzed reaction. Regio- and enantioselective allylic substitution of the unsymmetrical
phosphates with hydroxylamines was studied by using the iridium complex of chiral pybox ligand.
The aqueous-medium reaction with hydroxylamines proceeded smoothly in the presence of Ba(OH)2·H2O to give the branched products with good enantioselectivities.