Pd(II)‐Catalyzed Asymmetric [2+2] Annulation for the Construction of Chiral Benzocyclobutenes

Asymmetric de novo synthesis of benzocyclobutenes (BCBs) via catalytic intermolecular reaction is highly desired for efficient access to this important class of compounds, yet such a strategy remains unmet challenge. Here, we report a Pd/Pyrox‐catalyzed asymmetric [2+2] annulation between arylboronic acids and functionalized alkenes, providing an unprecedented efficient protocol to access various enantio‐enriched BCBs in a modular and versatile manner under mild conditions. A broad substrate scope with excellent enantioselectivity has been achieved under the current protocol. The isolation and characterization of the key chiral palladacycle intermediate, together with DFT calculations, provides strong evidence for the catalytic pathway including an enantiodetermining arylpalladation step.