10.1021/jo902165w.s002
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/2805595
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.