Excited-State Cu-BINAP Catalysis for Molecular Valorization

The use of visible light to drive chemical transformations has a history spanning over a century. However, the development of photo-redox catalysts to efficiently harness light energy is a more recent advancement, evolving over the past two decades. While ruthenium and iridium-based photocatalysts dominate due to their photostability, long excited-state lifetimes, and high redox potentials, concerns about sustainability and cost have shifted attention to first-row transition metals. Luminescent Cu(I) complexes have emerged as promising alternatives, offering open-shell reactivity and tunable photoelectrochemical properties. This review (i) provides an overview of the structural, photophysical, and electrochemical properties governing copper(I) complexes; (ii) highlights advances in Cu(I)-BINAP catalysis for carbon-carbon and carbon-heteroatom bond formations under mild conditions; and (iii) analyzes the trajectory of this catalytic system, addressing challenges and identifying opportunities for further development.