10.1021/jo902165w.s001 Matthew R. Smith Matthew R. Smith Alexander J. Blake Alexander J. Blake Christopher J. Hayes Christopher J. Hayes Malcolm F. G. Stevens Malcolm F. G. Stevens Christopher J. Moody Christopher J. Moody Carbene Reactivity of 4-Diazo-4<i>H</i>-imidazoles toward Nucleophiles and Aromatic Compounds American Chemical Society 2009 irradiation diazoimidazolecarboxylate Aromatic imidazoazocine Reactivity insertion hydrocarbon arylimidazole derivatives 7. Reaction pyridinium ylide 8 Carbene norcaradiene chloroimidazole Nucleophile solvent amines pyridine Diazo Dichloromethane CompoundsCarbene hexafluorobenzene imidazolylidene carbene trap 2009-12-18 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Carbene_Reactivity_of_4_Diazo_4_i_H_i_imidazoles_toward_Nucleophiles_and_Aromatic_Compounds/2805598 Carbenes derived from diazoimidazolecarboxylates <b>4</b> under thermal or photochemical conditions undergo O−H and N−H insertion reactions with alcohols and amines, respectively, in moderate yield, in competition with reduction in good H-donor solvents. Dichloromethane reacts to give the corresponding 4-chloroimidazole. Aromatic hydrocarbons are excellent traps for the imidazolylidene carbene and lead to a range of arylimidazole derivatives <b>7</b>. Reaction with pyridine leads to the first example of a pyridinium ylide <b>8</b> formed from an imidazolylidene carbene, whereas irradiation in hexafluorobenzene gives the imidazoazocine <b>11</b>, presumably by way of an initial norcaradiene intermediate.