Asymmetric Synthesis of Fluorinated Quaternary Stereogenic Centers Enabled by a Bispyrrolidine-Diboronate-Catalyzed exo -Selective Diels–Alder Reaction

The stereoselective construction of fluorinated architectures is of great importance in medicinal chemistry, as fluorination can profoundly improve the pharmacokinetic profiles of bioactive molecules. Nonetheless, the enantioselective synthesis of fluorine-containing natural product derivatives continues to pose a significant challenge. In this work, we describe a highly exo- and enantioselective Diels–Alder reaction enabled by a novel diboronate complex generated from bispyrrolidine diboronate (BPDB) in combination with Lewis and Brønsted acids. This strategy provides efficient access to structurally diverse fluorinated abietane diterpenes with high stereocontrol.