CuH-Catalyzed Regio- and Stereoselective Hydroalkoxylation of Styrenes with Acetal-Based Peroxides

An oxygen-umpolung-enabled, copper-catalyzed hydroalkoxylation reaction of styrenes has been developed. The key to success lies with the CF3-substituted electron-deficient acetal-based peroxides, which enables the chemo-, regio-, and stereoselective net hydroalkoxylation of alkene π-bonds under the initiation by CuH species. The use of a chiral bisphosphine ligand further enables the delivery of enantioenriched chiral ethers with good enantiomeric ratios.