Nickel binding enables isolation and reactivity of previously inaccessible 7-aza-2,3-indolynes

• 成果类型: Article
• 署名作者: Humke, Jenna N.; Belli, Roman G.; Plasek, Erin E.; Kargbo, Sallu S.; Ansel, Annabel Q.; Roberts, Courtney C.
• 署名单位: University of Minnesota System; University of Minnesota Twin Cities
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-11832
• DOI: 10.1126/science.adi1606
• 发表日期: 2024-04-26
• 页码: 408-414
• 关键词: molecular-structure; crystal-structure; aryne complexes; benzyne; metals; 7-azaindoles; heterocycles; mechanism; DESIGN

摘要

N-Heteroaromatics are key elements of pharmaceuticals, agrochemicals, and materials. N-Heteroarynes provide a scaffold to build these essential molecules but are underused because five-membered N-heteroarynes have been largely inaccessible on account of the strain of a triple bond in that small of a ring. On the basis of principles of metal-ligand interactions that are foundational to organometallic chemistry, in this work we report the stabilization of five-membered N-heteroarynes in the nickel coordination sphere. A series of 1,2-bis(dicyclohexylphosphino)ethane nickel 7-azaindol-2,3-yne complexes were synthesized and characterized crystallographically and spectroscopically. Ambiphilic reactivity of the nickel 7-azaindol-2,3-yne complexes was observed with multiple nucleophilic, electrophilic, and enophilic coupling partners.