Photosensitization enables Pauson-Khand-type reactions with nitrenes

• 成果类型: Article
• 署名作者: Li, Fang; Zhu, W. Felix; Empel, Claire; Datsenko, Oleksandr; Kumar, Adarsh; Xu, Yameng; Ehrler, Johanna H. M.; Atodiresei, Iuliana; Knapp, Stefan; Mykhailiuk, Pavel K.; Proschak, Ewgenij; Koenigs, Rene M.
• 署名单位: RWTH Aachen University; Goethe University Frankfurt; Enamine Ltd; Goethe University Frankfurt; Ministry of Education & Science of Ukraine; Taras Shevchenko National University of Kyiv
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-12678
• DOI: 10.1126/science.adm8095
• 发表日期: 2024-02-02
• 页码: 498-503
• 关键词: urea inhibitors; reactivity; reduction; diversity; DESIGN; silver; STATES; route

摘要

The Pauson-Khand reaction has in the past 50 years become one of the most common cycloaddition reactions in chemistry. Coupling two unsaturated bonds with carbon monoxide, the transformation remains limited to CO as a C1 building block. Herein we report analogous cycloaddition reactions with nitrenes as an N1 unit. The reaction of a nonconjugated diene with a nitrene precursor produces bicyclic bioisosteres of common saturated heterocycles such as piperidine, morpholine, and piperazine. Experimental and computational mechanistic studies support relaying of the diradical nature of triplet nitrene into the p-system. We showcase the reaction's utility in late-stage functionalization of drug compounds and discovery of soluble epoxide hydrolase inhibitors.