N-heterocyclic carbenes which readily add ammonia, carbon monoxide and other small molecules,

Abstract

N-Heterocyclic carbenes (NHCs) are extremely valuable as nucleophilic organocatalysts. They are widely applied as ligands in transition-metal catalysed reactions, where they are known as particularly potent σ-donors. They are commonly viewed as workhorses exhibiting reliable, but undramatic, chemical behaviour. The N → Ccarbene π-donation stabilises NHCs at the expense of low reactivity towards nucleophiles. In contrast to NHCs, stable (alkyl)(amino)carbenes exhibit spectacular reactivity, allowing, for example, the splitting of hydrogen and ammonia and the fixation of carbon monoxide. NHCs have been judged to be electronically not suitable for showing similar reactivity. Here, we demonstrate that a ferrocene-based NHC is able to add ammonia, methyl acrylate, tert-butyl isocyanide, and carbon monoxide—reactions typical of (alkyl)(amino)carbenes, but unprecedented for diaminocarbenes. We also show that even the simplest stable diaminocarbene, C(NiPr2)2, adds CO. This reaction affords a β-lactam by a subsequent intramolecular process involving a C–H activation. Our results shed new light on the chemistry of diaminocarbenes and offer great potential for synthetic chemistry and catalysis.