Journal of the American Chemical Society, Vol.116, No.9, 3684-3691, 1994
Hypervalent Iodine-Induced Nucleophilic-Substitution of Parasubstituted Phenol Ethers - Generation of Cation Radicals as Reactive Intermediates
A novel hypervalent iodine induced nucleophilic substitution of para-substituted phenol ethers in the presence of a variety of nucleophiles is described. UV and ESR spectroscopic studies indicate that this reaction proceeds via cation radicals, [ArH.+], as reactive intermediates generated by single-electron transfer (SET) from a charge-transfer (dT) complex of phenol ethers with phenyliodine(III) bis(trifluoroacetate) (PIFA). This is the first case that involves a radical intermediate on hypervalent iodine oxidations of aromatic compounds.
Keywords:ORGANIC-SYNTHESIS;AZACARBOCYCLIC SPIRODIENONES;OXIDATIVE CYCLIZATION;EFFICIENT CONVERSION;DISCORHABDIN-C;QUINOL ETHERS;KETO GROUPS;DERIVATIVES;CHEMISTRY;(DIACETOXYIODO)BENZENE