Piedra Helena F, Valdés Carlos, Plaza Manuel
Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica "Enrique Moles" and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Oviedo Julián Clavería 8 33006 Oviedo Spain
Chem Sci. 2023 May 11;14(21):5545-5568. doi: 10.1039/d3sc01724a. eCollection 2023 May 31.
The discovery of new activation modes for the creation of carbon-centered radicals is a task of great interest in organic chemistry. Classical activation modes for the generation of highly reactive radical carbon-centered intermediates typically relied on thermal activation of radical initiators or irradiation with unsafe energetic UV light of adequate reaction precursors. In recent years, photoredox chemistry has emerged as a leading strategy towards the catalytic generation of C-centered radicals, which enabled their participation in novel synthetic organic transformations which is otherwise very challenging or even impossible to take place. As an alternative to these activation modes for the generation of C-centered radicals, the pursuit of greener, visible-light initiated reactions that do not necessitate a photoredox/metal catalyst has recently caught the attention of chemists. In this review, we covered recent transformations, which rely on photoactivation with low-energy light of a class of EDA complexes, known as halogen-bonding adducts, for the creation of C-centered radicals.
发现用于生成碳中心自由基的新活化模式是有机化学中一项极具吸引力的任务。生成高反应活性的碳中心自由基中间体的经典活化模式通常依赖于自由基引发剂的热活化或用不安全的高能紫外光照射合适的反应前体。近年来,光氧化还原化学已成为催化生成碳中心自由基的主要策略,这使得它们能够参与新型有机合成转化,而这些转化在其他情况下极具挑战性甚至无法发生。作为这些生成碳中心自由基的活化模式的替代方法,追求更绿色、无需光氧化还原/金属催化剂的可见光引发反应最近引起了化学家的关注。在本综述中,我们涵盖了最近的一些转化反应,这些反应依赖于一类称为卤素键加合物的电子给体-受体(EDA)配合物的低能光光活化来生成碳中心自由基。