Nonheme Manganese-Catalyzed Achmatowicz Rearrangement Using H₂O₂ as the Oxidant

The growing importance of the Achmatowicz rearrangement in synthetic chemistry has heightened the demand for environmentally friendly catalytic strategies. Conventional methods relying on stoichiometric oxidants such as m-CPBA or NBS suffer from low atom economy and generate stoichiometric organic waste. Inspired by the efficiency of chloroperoxidase (CPO) in mediating Achmatowicz rearrangement through dioxygen (O2) activation, we report a bioinspired manganese catalytic system. This approach employs environmentally benign hydrogen peroxide (H2O2) as the oxidant under mild conditions, enabling both O-Achmatowicz and Aza-Achmatowicz rearrangements with excellent functional group tolerance. The present work offers a green and efficient alternative for this important class of transformations.