Efficient Pd-Catalyzed Direct Coupling of Aryl Chlorides with Alkyllithium Reagents.

Organolithium compounds are amongst the most important organometallic reagents and frequently used in difficult metallation reactions. However, their direct use in the formation of C-C bonds is less established. Although remarkable advances in the coupling of aryllithium compounds have been achieved, Csp -Csp coupling reactions are very limited.

Palladium Complexes Based on Ylide-Functionalized Phosphines (YPhos): Broadly Applicable High-Performance Precatalysts for the Amination of Aryl Halides at Room Temperature.

Palladium allyl, cinnamyl, and indenyl complexes with the ylide-substituted phosphines Cy P -C (R)PCy (with R=Me (L1) or Ph (L2)) and Cy P -C (Me)PtBu (L3) were prepared and applied as defined precatalysts in C-N coupling reactions. The complexes are highly active in the amination of 4-chlorotoluene with a series of different amines. Higher yields were observed with the precatalysts in comparison to the in situ generated catalysts.