He Yijie, Lyu Yichong, Tymann David, Antoni Patrick W, Hansmann Max M
Fakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Str. 6, 44227, Dortmund, Germany.
Angew Chem Int Ed Engl. 2025 Jan 15;64(3):e202415228. doi: 10.1002/anie.202415228. Epub 2024 Oct 30.
The cleavage of carbophosphinocarbenes and carbodicarbenes with nitrous oxide (NO) leads to the formation of room-temperature stable diazoalkenes. The utility of PhP/N and NHC/N ligand exchange reactions were demonstrated by accessing novel benzimidazole- and benzothiazole derived diazoalkenes, which are not accessible by the current state-of-the-art methods. The stable diazoalkenes subsequently allow further ligand exchange reactions at C(0) with carbon monoxide, isocyanide, or a diamidocarbene (DAC). Overall, the combination of hitherto unknown NHC/N and N/L (L = DAC, CO, R-NC) ligand exchange reactions at a C(0) center allow the selective functionalization of the carbodicarbene ligand structure which represents a new methodology to rapidly assemble novel carbodicarbenes or cumulenic compounds.
碳膦亚甲基和碳二亚甲基与一氧化二氮（NO）的裂解反应生成了室温稳定的重氮烯烃。通过获得新型苯并咪唑和苯并噻唑衍生的重氮烯烃，证明了PhP/N和NHC/N配体交换反应的实用性，而这些重氮烯烃是目前最先进的方法无法获得的。稳定的重氮烯烃随后允许在C(0)处与一氧化碳、异腈或二酰胺卡宾（DAC）进行进一步的配体交换反应。总体而言，在C(0)中心进行的迄今未知的NHC/N和N/L（L = DAC、CO、R-NC）配体交换反应相结合，能够对碳二亚甲基配体结构进行选择性功能化，这代表了一种快速组装新型碳二亚甲基或累积烯烃化合物的新方法。
