Litcius/Paper detail

Cleavage of Carbodicarbenes with N <sub>2</sub> O for Accessing Stable Diazoalkenes: Two‐Fold Ligand Exchange at a C(0)‐Atom

Yijie He, Yichong Lyu, David Tymann, Patrick W. Antoni, Max M. Hansmann

2024Angewandte Chemie International Edition21 citationsDOIOpen Access PDF

Abstract

Abstract The cleavage of carbophosphinocarbenes and carbodicarbenes with nitrous oxide (N 2 O) leads to the formation of room‐temperature stable diazoalkenes. The utility of Ph 3 P/N 2 and NHC/N 2 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 2 and N 2 /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.

Topics & Concepts

BenzimidazoleChemistryLigand (biochemistry)BenzothiazoleCleavage (geology)IsocyanideCarbon monoxideCarbon atomSurface modificationStereochemistryCatalysisOrganic chemistryMaterials scienceReceptorPhysical chemistryRing (chemistry)BiochemistryFracture (geology)Composite materialCyclopropane Reaction MechanismsCatalytic Cross-Coupling ReactionsN-Heterocyclic Carbenes in Organic and Inorganic Chemistry