A brief, efficient method has been developed for the removal of the allyl protecting group from allyl carboxylic esters using a Co­(II)/TBHP/(Me2SiH)2O catalytic system. This facile strategy displays excellent chemoselectivity, functional group tolerance, and high yields. This transformation probably occurs through the hydrogen atom transfer process, and a Co­(III)–six-membered cyclic intermediate is recommended.

A simple, mild and efficient method for the isomerization of 2‐substituted allyl ethers has been developed by cobalt‐catalyzed hydrogen atom transfer (HAT) process. The trivalent cobalt complex oxidized in‐situ by tert‐butyl hydroperoxide (tBuOOH) exhibits higher catalytic activity than prefabricated trivalent cobalt catalysts. This facile protocol displays excellent chemoselectivity, good functional group tolerance and high yields. The obtained vinyl ethers can be easily hydrolyzed by N‐iodosuccinimide/water to afford corresponding phenols or alcohols.