Nitrate reduction enables safer aryldiazonium chemistry

• 成果类型: Article
• 署名作者: Mateos, Javier; Schulte, Tim; Behera, Deepak; Leutzsch, Markus; Altun, Ahmet; Sato, Takuma; Waldbach, Felix; Schnegg, Alexander; Neese, Frank; Ritter, Tobias
• 署名单位: Max Planck Society; RWTH Aachen University; Max Planck Society
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-9805
• DOI: 10.1126/science.adn7006
• 发表日期: 2024-04-26
• 页码: 446-452
• 关键词: aryl diazonium salts; sulfur-dioxide; basis-sets; kinetics; water; reactivity; sandmeyer; STABILITY; mechanism; oxidation

摘要

Aryldiazonium salts remain a staple in organic synthesis and are still prepared largely in accord with the protocol developed in the 19th century. Because of the favorable reactivity that often cannot be achieved with other aryl(pseudo)halides, diazonium chemistry continues to grow. Facile extrusion of dinitrogen contributes to the desired reactivity but is also reason for safety concerns. Explosions have occurred since the discovery of these reagents and still result in accidents. In this study, we report a diazonium chemistry paradigm shift based on nitrate reduction using thiosulfate or dihalocuprates as electron donors that avoids diazonium accumulation. Because nitrate reduction is rate-limiting, aryldiazoniums are produced as fleeting intermediates, which results in a safer and often more efficient deaminative halogenation in a single step from anilines.