Organic Chemistry

Umpolung Strategy for Arene C–H Etherification Leading to Functionalized Chromanes Enabled by I(III) N-Ligated Hypervalent Iodine Reagents

Authors

Abstract

The direct formation of aryl C–O bonds via the intramolecular dehydrogenative coupling of a C–H bond and a pendant alcohol represents a powerful synthetic transformation. Herein, we report a method for intramolecular arene C–H etherification via an umpoled alcohol cyclization mediated by an I(III) N-HVI reagent. This approach provides access to functionalized chromane scaffolds from primary, secondary and tertiary alcohols via a cascade cyclization-iodonium salt formation, the latter providing a versatile functional handle for downstream derivatization. Computational studies support initial formation of an umpoled O-intermediate via I(III) ligand exchange, followed by competitive direct and spirocyclization/1,2-shift pathways.

Content

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Supplementary material

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Supporting Information: Umpolung Strategy for Arene C–H Etherification Leading to Functionalized Chromanes Enabled by I(III) N-Ligated Hypervalent Iodine Reagents
Synthesis of Reagents, Substrates, General Procedures. Characterization and Spectral Data for Novel Compounds. Supplemental Screening and Mechanistic Studies.