Photochemical phosphorus-enabled scaffold remodeling of carboxylic acids

• 成果类型: Article
• 署名作者: Peng, Qiupeng; Hwang, Meemie U.; Renteria-Gomez, Angel; Mukherjee, Poulami; Young, Ryan M.; Qiu, Yunfan; Wasielewski, Michael R.; Gutierrez, Osvaldo; Scheidt, Karl A.
• 署名单位: Northwestern University; Texas A&M University System; Texas A&M University College Station; Northwestern University
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-10159
• DOI: 10.1126/science.adr0771
• 发表日期: 2024-09-27
• 页码: 1471-1477
• 关键词: density-functional theory; molecular-energies; basis-sets; catalysis; photoredox; complexes; imines

摘要

The excitation of carbonyl compounds by light to generate radical intermediates has historically been restricted to ketones and aldehydes; carboxylic acids have been overlooked because of high energy requirements and low quantum efficiency. A successful activation strategy would necessitate a bathochromic shift in the absorbance profile, an increase in triplet diradical lifetime, and ease of further functionalization. We present a single-flask transformation of carboxylic acids to acyl phosphonates that can access synthetically useful triplet diradicals under visible light or near-ultraviolet irradiation. The use of phosphorus circumvents unproductive Norrish type I processes, promoting selectivity that enables hydrogen-atom transfer reactivity. Use of this strategy promotes the efficient scaffold remodeling of carboxylic acids through various annulation, contraction, and expansion manifolds.