Photocatalytic Deoxygenative Hydroalkylation Enables Modular Access to CF3-Substituted Oxetanes.

CF3-substituted oxetanes are emerging tert-butyl bioisosteres of growing interest in medicinal chemistry, yet their synthesis remains challenging. Here, we report a visible-light photocatalytic hydroalkylation of readily available α-CF3 oxetane benzoates with unactivated alkenes. Enabled by formate-mediated reductive generation of α-CF3 oxetanyl radicals, the reaction proceeds under mild conditions with broad substrate scope and functional-group tolerance, furnishing diverse CF3-substituted oxetanes from simple starting materials. This modular protocol expands access to these underexplored bioisosteric motifs and facilitates their incorporation into medicinally relevant molecules.