Unlocking the Potential of Organoaluminum Reagents for Versatile C─C Couplings Using YPhos‐Pd Catalysts

We report a general and efficient protocol for the palladium‐catalyzed cross‐coupling of aryl chlorides with a broad range of organoaluminum nucleophiles, enabled by strongly donating ylide‐functionalized phosphines (YPhos). Unlike other earth‐abundant organometallic reagents, the protocol demonstrates broad functional group tolerance, even allowing for late‐stage functionalizations of complex molecules. In general, high selectivities and yields are achieved, while maintaining the high reactivity characteristics of this class of compounds even at room temperature. The presented protocol highlights the key advantages of this thus far underestimated class of nucleophiles in coupling chemistry and illustrates both the strengths and limitations of in situ generated alkyl‐, aryl‐, alkenyl‐, and alkynylaluminum reagents.