Enantioconvergent Cross-Electrophile Coupling of 2-Aryloxetanes with Aryl and Vinyl Halides, or Anhydrides

Catalytic enantioselective transformations of small heterocycles continue to be the fundamental goal in synthetic chemistry. While considerable advancements have been achieved in catalytic cross-electrophile coupling of epoxides, the analogous potential to oxetanes remains a substantially untapped frontier, probably due to their high activation energy. Herein, an unprecedented Ti/Ni/photoredox-catalyzed stereoconvergent cross-electrophile coupling of 2-aryloxetanes with (hetero)aryl and vinyl halides, or anhydrides, was developed, providing an appealing approach for the synthesis of diverse γ,γ-disubstituted alcohols or esters suitable for good yields with high enantioselectivity (>60 examples, up to 89% yield, 97% ee). The coupling products could be readily transformed to the chiral intermediates of marketed drugs sertraline and indatraline, as well as a modulator of CCR5 receptor activity.