Coupling of Aryl Chlorides with Lithium Nucleophiles Enabled by Molecularly Defined Alkynyllithium Palladium Catalysts.

Palladium‐catalyzed cross‐couplings of aryl chlorides usually call for bulky, electron‐rich ligands such as phosphines or heterocyclic carbenes. We have now found that similarly powerful cross‐coupling catalysts are obtained by the reaction of palladium salts with alkynyllithium reagents. The species initially formed in this process was characterized as a dilithium tetraalkinyl palladate complex. It catalyzes the coupling of aryl chlorides with the lithium salts of various terminal alkynes to give alkynyl arenes. The isolated Li‐alkynyl‐Pd complex also efficiently promotes the reaction of aryl, and allyl chlorides with (hetero)aryl‐, alkyl‐, and allyllithium compounds as well as lithium amides. None of these reactions proceeded in the presence of palladium salts alone. The preparative utility of this approach was demonstrated by the synthesis of 49 molecules, including pharmaceutically relevant compounds. [ABSTRACT FROM AUTHOR]