Oxyalkylation of Alkenes via Triple Radical Sorting

Alkene difunctionalization enables rapid access to structurally diverse chemical space. However, oxyalkylation, where an oxygenated group and an alkyl fragment are simultaneously installed across an alkene, remains underexplored. Whereas formal Markovnikov oxyalkylation has been known for several decades, the development of a general method with reversed selectivity remains a notable challenge. Such a transformation would streamline the synthesis of pharmaceutically relevant scaffolds including hindered all-carbon quaternary centers. Herein, we report a three-component oxyalkylation of unactivated alkenes with anti-Markovnikov selectivity via a metallaphotoredox-based 'triple radical sorting' mechanism. This protocol couples alkenes with benzoic acids and redox-active esters in a single step and accommodates a range of substrates including complex, drug-like molecules. The reaction is readily scalable and can be adapted to a one-flask oxyalkylation/deprotection sequence to directly furnish free alcohols without intermediate purification.