Photosensitization enables Pauson-Khand-type reactions with nitrenes

• Published in: Science (American Association for the Advancement of Science) Vol. 383; no. 6682; pp. 498 - 503
• Main Authors: 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.
• Format: Journal Article
• Language: English
• Published: WASHINGTON Amer Assoc Advancement Science 02.02.2024; The American Association for the Advancement of Science
• Subjects: Carbon monoxide; Catalysts; Chemical bonds; Cobalt; Cobalt compounds; Multidisciplinary Sciences; Organic compounds; Photosensitization; Science & Technology; Science & Technology - Other Topics; ROUTE; DESIGN; STATES; REDUCTION; SILVER; REACTIVITY; UREA INHIBITORS; DIVERSITY
• ISSN: 0036-8075; 1095-9203
• DOI: 10.1126/science.adm8095

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.