Cyclic (alkyl)(amino)carbenes with a six-membered backbone were prepared. Compared to their five-membered analogues, they feature increased % Vbur and enhanced donor and acceptor properties, as evidenced by the observed n → π* transition trailing into the visible region. The high ambiphilic character even allows for the intramolecular insertion of the carbene into an unactivated C(sp3)-H bond. When used as ligands, they outcompete the five-membered analogues in the palladium-mediated α-arylation of ketones with aryl chlorides.