Boron Amidate as a Modular Anionic Catalyst for Sequential Electron-Donor/Hydrogen-Atom-Transfer Catalysis.

Electron donor-acceptor (EDA) complex excitation has emerged as a powerful strategy for generating reactive radical species without external photocatalysts. However, the rational design of catalysts that integrate electron transfer with hydrogen atom transfer (HAT) remains underdeveloped. Herein, we report a modular anionic boron amidate that functions as a dual electron-donor/HAT catalyst within a single molecular framework. The π-conjugated anionic structure enables efficient donor-acceptor assembly, while structural modification at the nitrogen center allows systematic tuning of the donor strength, Brønsted acidity, and N-H bond dissociation free energy (BDFE). This catalyst enables EDA-driven radical generation followed by productive HAT, as demonstrated in Giese-type C-(sp3)-H functionalization. Furthermore, a Minisci-type reaction is achieved through modulation of the proton-donating ability of the boron amide, which proceeds under oxidant-free conditions and is presumably sustained by aerobic oxidation. These results establish a modular design strategy for anionic molecular catalysts that orchestrate electron transfer and HAT processes, thereby providing a framework for EDA-based catalytic transformations.