Cleavage of carbodicarbenes with N2O for accessing stable diazoalkenes: two-fold ligand exchange at a C(0)-atom

Abstract

The cleavage of carbophosphinocarbenes and carbodicarbenes with nitrous oxide (N2O) leads to the formation of room-temperature stable diazoalkenes. The utility of Ph3P/N2 and NHC/N2 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/N2 and N2/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.