Rhodium‐Catalyzed Addition of Aryl Boronic Acids to 2,2‐Disubstituted Malononitriles

β‐Ketonitriles bearing a quaternary carbon at the 2‐position were prepared through Rh‐catalyzed addition of aryl boronic acids to 2,2‐disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro‐Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted malononitriles, providing a diverse array of β‐ketonitriles. The products could be further derivatized to valuable chiral α,α‐disubstituted‐β‐aminonitriles through addition reactions to the corresponding N ‐tert ‐butanesulfinyl imines.