A Crystalline (Amino)(chloro)Carbene: A Platform for Nucleophilic Substitution at a Carbene Center

ABSTRACT Halogenocarbenes have attracted significant interest for almost a century because they combine classical singlet carbene reactivity with the presence of a readily substituted halogen group. Before this work, no halogenocarbenes had been isolated and taming their instability remained a synthetic challenge. This report describes the preparation of room temperature stable (amino)(chloro)carbenes and examples of their substitution chemistry at the carbene center, unlocking access to a wide range of acyclic carbenes.