Rhodium(II)‐Catalyzed Selective C(sp3)−H Amination of Alkanes

The development of an efficient catalytic system enabling the conversion of alkanes to valuable nitrogen‐containing building blocks is reported. Light alkanes can be selectively functionalized by an intermolecular C(sp3)−H amination reaction that proceeds at room temperature in the presence of only 1 mol % of a dirhodium(II) complex. Selective amination of tertiary C(sp3)−H within acyclic or cyclic alkanes used as limiting components leads to the corresponding amides isolated with yields in the 51–96 % range. The reaction, that can be performed on a gram‐scale, applies with equal levels of efficiency and selectivity to more complex hydrocarbons. Rhodium(II)‐catalyzed intermolecular C(sp3)−H amination with sulfamates allows to functionalize alkanes used as the limiting component, selectively at tertiary centers. Valuable nitrogen‐containing building blocks can be isolated in good to excellent yields.