Asymmetric Synthesis of Fluorinated Cyclobutenes Containing Quaternary Carbon Stereocenters by Rh‐Catalyzed Defluoroarylation

Fluorinated four‐membered rings represent valuable structural motifs in bioactive molecules and pharmaceuticals; however, the asymmetric synthesis of such fluorinated frameworks bearing chiral quaternary carbon centers has not yet been achieved. Herein, we report a Rh‐catalyzed enantioselective defluoroarylation of gem ‐difluorinated cyclobutenes with aryl boronates, enabling the asymmetric construction of fluorinated cyclobutenes bearing chiral quaternary carbon centers with high enantioselectivity via an addition/β‐fluoride elimination process. In situ treatment with an additional distinct aryl boronate enables one‐pot bis‐defluoroarylation to give unsymmetrical diarylated cyclobutenes.