Abstract
The nucleophilic iron complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) is an active catalyst in C−H‐amination but also in proton‐transfer catalysis. Herein, we describe the successful use of this complex as a proton‐transfer catalyst in the cyclocondensation reaction between azides and ketones to the corresponding 1,2,3‐triazoles. Cross‐experiments indicate that the proton‐transfer catalysis is significantly faster than the nitrene‐transfer catalysis, which would lead to the C−H amination product. An example of a successful sequential Dimroth triazole–indoline synthesis to the corresponding triazole‐substituted indolines is presented.
A Fe‐rocious catalyst: The nucleophilic iron complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the Dimroth cyclocondensation between arylazides and substituted ketones to the corresponding triazoles. This process can be coupled to the TBA[Fe]‐catalyzed C(sp3)−H amination and provides straightforward access to highly decorated N‐heterocyclic systems.