In the last decade the dearomatization of phenolic species has been the subject of profound investigations. It constitutes an attractive strategy to access highly functionalized products that can serve as building blocks for further transformations, such as 1,2- and 1,4-additions, epoxidation, or Corey-Chaykovsky and Diels-Alder reactions. An important class of phenol dearomatizations are the oxidations promoted by hypervalent iodine(III) reagents. In particular, a number of enantioselective processes employing only catalytic amounts of chiral iodoarenes has been reported, wherein various nucleophiles are added to phenolic ring (e.g., water, carboxylates).<br/><br/>In this context, we have developed an enantioselective, oxidative dearomatization of phenols coupled with the addition of methanol. The reaction employs chiral iodoarene catalyst derived from 2-iodoresorcinol and <i>m</i>CPBA as a terminal oxidant. This method allows for the methoxylation of diverse phenols, containing a range of substituents, in 50-90% yield and 30-60% ee.

Enantioselective oxidative dearomatizating methoxylation of phenols catalyzed by chiral iodoarenes

ACS Spring 2022

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