Mechanism of Rh₂(II)-Catalyzed Indole Formation: The Catalyst Does Not Control Product Selectivity

Abstract

Possible mechanisms for Rh-promoted indole formation from vinyl/azidoarenes were examined computationally, and a mechanism is proposed in which the Rh catalyst promotes generation of a nitrene but is not directly involved in cyclization.

Enantioselective synthesis of isochromans and tetrahydroisoquinolines by C–H insertion of donor/donor carbenes

“…44 This model suggests that the metal catalyst is not essential in the Stevens rearrangement step. 45…”

Palladium‐Catalyzed Intramolecular C–H Amination in Water

“…Following Driver's reports on Rh catalysis[10a] and Plietker's recent report on Fe‐catalyzed[10b] carbazole and indole synthesis,, we began our investigation by screening reaction catalysts in water (Table ). With 2‐azidobiphenyls as the substrates, the reactions may proceed under non‐oxidative conditions with N 2 as the sole byproduct to form functionalized carbazoles that are of interest because of their various biological activities Initial results with different metal catalysts by using 2‐azidobiphenyl ( 1a ) as the substrate are shown in Table (Entries 1–15).…”

Density functional calculations for Rh(I)‐catalyzed C–C bond activation of siloxyvinylcyclopropanes and diazoesters

“…Single‐point energy calculations were carried out at the B3LYP/6‐311++G(d,p) level (LANL2DZ(f) for Rh) to refine the solvent effect of 1,4‐dioxane using the Cramer–Truhlar continuum solvation model (SMD) of the self‐consistent reaction field approach. Similar computations have been used in recent studies …”