Second Comes First: Switching Elementary Steps in Palladium-Catalyzed Cross-Coupling Reactions.

ABSTRACT: The electron-poor palladium(0) complex L₃ Pd (L=tris[3,5-bis(trifluoromethyl)phenyl]phosphine) reacts with Grignard reagents RMgX and organolithium compounds RLi via transmetalation to furnish the anionic organopalladates [L₂ PdR]^- , as shown by negative-ion mode electrospray-ionization mass spectrometry. These palladates undergo oxidative additions of organyl halides R'X (or related S_N 2-type reactions) followed by further transmetalation. Gas-phase fragmentation of the resulting heteroleptic palladate(II) complexes results in the reductive elimination of the cross-coupling products RR'. This reaction sequence corresponds to a catalytic cycle, in which the order of the elementary steps of transmetalation and oxidative addition is switched relati

SUBMITTER: Kolter M 

PROVIDER: S-EPMC7540703 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature