Excited-state configuration of nitroarenes enables oxidative cleavage of aromatics over alkenes

• 成果类型: Article
• 署名作者: Olivier, Wesley J.; Blyszczyk, Piotr; Arpa, Enrique M.; Hitoshio, Kenshiro; Gomez-Mendoza, Miguel; O'shea, Victor de la Pena; Marchand, Isabelle; Poisson, Thomas; Ruffoni, Alessandro; Leonori, Daniele
• 署名单位: RWTH Aachen University; IMDEA Energy; Centre National de la Recherche Scientifique (CNRS); Universite de Rouen Normandie; University of Kiel
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-10532
• DOI: 10.1126/science.ads3955
• 发表日期: 2025-03-14
• 页码: 1167-1174
• 关键词: independent chemical-shifts; kinetics; photosubstitution; photochemistry; OPPORTUNITIES; derivatives; potentials; resonance; electron; ethers

摘要

The ozonolytic deconstruction of aromatics remains a challenge in organic chemistry. Ozone preferentially reacts with alkenes over arenes, meaning that once the initial aromatic cleavage occurs, the dearomatized products are inherently more reactive than the starting materials. Consequently, the process cannot be halted, resulting in full oxidation. Addressing this challenge requires subverting intrinsic rules of chemoselectivity to transform a less reactive substrate in the presence of a more reactive one. We demonstrate that this concept can be achieved by using photoexcited nitroarenes. Crucial to the success of this chemoselective process is the use of a nitroarene that is preferentially excitable to a triplet pi,pi* state over the n,pi* state. This switch in excited-state configuration provides an otherwise inaccessible manifold, in which oxidative cleavage is diverted toward aromatics in the presence of alkenes.