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Examination of the mechanism of Rh(2)(II)-catalyzed carbazole formation using intramolecular competition experiments.

ABSTRACT: 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 sigma(+) values produced a plot with two intersecting lines with opposite rho values. These data suggest that electronic donation by the biaryl pi-system accelerates the formation of rhodium nitrenoid and that C-N bond formation occurs through a 4pi-electron-5-atom electrocyclization.

SUBMITTER: Stokes BJ

PROVIDER: S-EPMC2883892 | biostudies-literature | 2009 Sep

REPOSITORIES: biostudies-literature

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Examination of the mechanism of Rh(2)(II)-catalyzed carbazole formation using intramolecular competition experiments.

Stokes Benjamin J BJ Richert Kathleen J KJ Driver Tom G TG

The Journal of organic chemistry 20090901 17

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 sigma(+) values produced a plot with two intersecting lines with opposite rho values. These data suggest that electronic donation by the biaryl pi-system acce ...[more]

PMID: 19663433

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