1174572-95-2Relevant academic research and scientific papers
Examination of the mechanism of Rh2(II)-catalyzed carbazole formation using intramolecular competition experiments
Stokes, Benjamin J.,Richert, Kathleen J.,Driver, Tom G.
supporting information; experimental part, p. 6442 - 6451 (2009/12/24)
(Chemical Equation Presented) The use of a rhodium(II) carboxylate catalyst enables the mild and stereoselective formation of carbazoles from biaryl azides. Intramolecular competition experiments of triaryl azides suggested the source of the selectivity. A primary intramolecular kinetic isotope effect was not observed, and correlation of the product ratios with Hammett σ+ values produced a plot with two intersecting lines with opposite ρ values. These data suggest that electronic donation by the biaryl π-system accelerates the formation of rhodium nitrenoid and that C-N bond formation occurs through a 4π-electron-5-atom electrocyclization.
