美国科罗拉多州立大学Garret M. Miyake团队揭示了质子耦合电子转移的高效超还原性有机光氧化还原催化减轻了反向电子转移。该研究于2025年6月19日发表于在《科学》杂志上。

可见光驱动的光还原催化通过实现更温和的反应条件和解锁不同的反应机制来改善化学合成。尽管有变革性的影响，可见光光氧化还原催化仍然受到光子能量的热力学限制和非生产性反电子转移引起的效率低下的限制，这两种情况在热力学要求高的反应中尤为明显。 

研究组介绍了一种有机光氧化还原催化剂体系，该体系克服了这些障碍，以驱动需要超还原能力的化学转化。这一进步是通过将两个光子的能量耦合到一个化学还原中来实现的，而通过催化剂设计中嵌入的独特的质子耦合电子转移机制来缓解背电子转移的效率低下。通过在广泛的具有挑战性的芳烃还原中的有效应用，研究组证明了这种有机催化剂体系的超还原能力。

附：英文原文

Title: Efficient super-reducing organic photoredox catalysis with proton-coupled electron transfer mitigated back electron transfer

Author: Amreen K. Bains, Arindam Sau, Brandon S. Portela, Kajal Kajal, Alexander R. Green, Anna M. Wolff, Ludovic F. Patin, Robert S. Paton, Niels H. Damrauer, Garret M. Miyake

Issue&Volume: 2025-06-19

Abstract: Photoredox catalysis driven by visible light has improved chemical synthesis by enabling milder reaction conditions and unlocking distinct reaction mechanisms. Despite the transformative impact, visible-light photoredox catalysis remains constrained by the thermodynamic limits of photon energy and inefficiencies arising from unproductive back electron transfer, both of which become particularly pronounced in thermodynamically demanding reactions. In this work, we introduce an organic photoredox catalyst system that overcomes these obstacles to drive chemical transformations that require super-reducing capabilities. This advancement is accomplished by coupling the energy of two photons into a single chemical reduction, whereas inefficiencies from back electron transfer are mitigated through a distinct proton-coupled electron transfer mechanism embedded in the catalyst design. The super-reducing capabilities of this organic catalyst system are demonstrated through efficient application in a broad scope of challenging arene reductions.

DOI: adw1648

Source: https://www.science.org/doi/10.1126/science.adw1648