ChemInform Abstract: Hypervalent (tert‐Butylperoxy)iodanes Generate Iodine‐Centered Radicals at Room Temperature in Solution: Oxidation and Deprotection of Benzyl and Allyl Ethers, and Evidence for Generation of α‐Oxy Carbon Radicals.

Abstract

The title iodane oxidizes benzyl and allyl ethers to the esters even at room temp. in the presence of alkali metal carbonates. Since this reaction is compatible with other protecting groups and because esters are readily hydrolyzed under basic conditions, this reaction offers a new method for the deprotection of benzyl and allyl ethers. Kinetic and mechanistic considerations reveal that the oxidation with the iodane occurs with activated C-H bonds generating α-oxy carbon-centered radicals, which can be detected by nitroxyl radical trapping.-(OCHIAI, M.; ITO, T.; TAKAHASHI, H.; NAKANISHI, A.; TOYONARI, M.; SUEDA, T.; GOTO, S.; SHIRO, M.; J.