Generating Active “L-Pd(0)” via Neutral or Cationic π-Allylpalladium Complexes Featuring Biaryl/Bipyrazolylphosphines: Synthetic, Mechanistic, and Structure–Activity Studies in Challenging Cross-Coupling Reactions
2015/06/02 by A. J. DeAngelis, Andrew DeAngelis, Peter G. Gildner +2 · 195 citations
Chemistry · #Catalysis #Catalytic Cross-Coupling Reactions #Catalytic C–H Functionalization Methods #Catalytic cycle #Cationic polymerization #Chemistry #Combinatorial chemistry #Coupling reaction #Heteroatom #Ligand (biochemistry) #Organic chemistry #Organoboron and organosilicon chemistry #Polymer chemistry #Receptor #Stereochemistry
paper · doi:10.1021/acs.joc.5b01005
published in The Journal of Organic Chemistry 80(13), 6794-6813 (American Chemical Society)
openalex publication_date 2015/06/02 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
Abstract
Two new classes of highly active yet air- and moisture-stable π-R-allylpalladium complexes containing bulky biaryl- and bipyrazolylphosphines with extremely broad ligand scope have been developed. Neutral π-allylpalladium complexes incorporated a range of biaryl/bipyrazolylphosphine ligands, while extremely bulky ligands were accommodated by a cationic scaffold. These complexes are easily activated under mild conditions and are efficient for a wide array of challenging C-C and C-X (X = heteroatom) cross-coupling reactions. Their high activity is correlated to their facile activation to a 12-electron-based "L-Pd(0)" catalyst under commonly employed conditions for cross-coupling reactions, noninhibitory byproduct release upon activation, and suppression of the off-cycle pathway to form dinuclear (μ-allyl)(μ-Cl)Pd2(L)2 species, supported by structural (single crystal X-ray) and kinetic studies. A broad scope of C-C and C-X coupling reactions with low catalyst loadings and short reaction times highlight the versatility and practicality of these catalysts in organic synthesis.
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