title: Cycloelimination of imidazolidin-2-ylidene N-heterocyclic carbenes: mechanism and insights into the synthesis of stable "NHC-CDI" amidinates.
abstract: We report the discovery that 1,3-bis(aryl)imidazolidin-2-ylidenes, one of the most widely studied classes of N-heterocyclic carbenes (NHCs), undergo quantitative conversion to zwitterionic "NHC-CDI" amidinates upon heating to ≈100 °C in solution. The mechanism of this novel NHC decomposition process is studied in detail. These studies enabled the rational synthesis of a new class of bench stable amidinates from a panel of NHCs and carbodiimides. We expect these constructs to find utility in a variety of applications.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139 (USA).
authors.forename: Aleksandr V
authors.initials: AV
authors.lastname: Zhukhovitskiy
authors.forename: Julie
authors.initials: J
authors.lastname: Geng
authors.forename: Jeremiah A
authors.initials: JA
authors.lastname: Johnson
mesh_terms: D000578:Amidines / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D007093:Imidazoles / Q000138:chemical synthesis / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular
chemical_list: D000578:Amidines; D007093:Imidazoles; C030011:carbene; D008697:Methane
keywords: amidinate; carbene; carbodiimide; cycloelimination; decomposition; pericyclic reaction