Phosphorinanes as Ligands for Palladium-Catalyzed Cross-Coupling Chemistry

Abstract

[structure: see text] Phosphorinanes are presented as a class of phosphine ligand suitable for organopalladium cross-coupling chemistry. Prepared via a direct double Michael addition of a monoalkyl- or arylphosphine to phorone followed by a Wolf-Kishner reduction, phosphorinanes are relatively inexpensive to manufacture and allow modification of one of the alkyl moieties permitting steric and electronic fine-tuning of the ligands. Library screening and applications of these ligands in the Suzuki, Sonogashira, ketone arylation, and aryl amination reactions are presented.

Carbene adduct of cyclopalladated ferrocenylimine as an efficient catalyst for the amination of aryl chlorides

“…In case of orthosubstituted phenyl chlorides, high yields of coupled amines were obtained (Table 7, entries 10,11). In case of aryl chlorides without ortho-substituent, both mono and di-substituted amines were obtained (Table 7, entries 8,9). Overall, the results above-mentioned that palladacycle 2 is clearly comparable in efficacy to other popular catalysts or ligands currently employed.…”

“…Not surprisingly, a plethora of palladium catalyst systems, featuring a palladium-bound ligand, are now accessible for accomplishing the transformation involving aryl chlorides. Typically, electron-rich sterically hindered phosphine ligands such as trialkylphosphines [2], aryldialkylphosphines [3][4][5], ferrocenyldialkylphosphines [6], dialkylphosphinous acids [7], bicyclic triaminophosphines [8] and phosphorinanes [9], have been investigated in these reactions. And a number of reports have shown that Pd complexes derived from sterically hindered and electron-rich phosphines are effective catalysts for this transformation [10].…”

“…Selected bond distances (Å ) and angles (°): Pd1-C6 1.983(4), Pd1-C20 1.998(3), Pd1-Cl1 2.379(1), Pd1-N1 2.114(3); C6-Pd1-C20 96.46(15), C6-Pd1-Cl1 170.94(12), C6-Pd1-N1 79.83(14), C20-Pd1-Cl1 90.47(15), C20-Pd1-N1 175.78(13), N1-Pd1-Cl1 93.01(9).…”

Palladium‐Katalysatorsysteme für die Synthese von konjugierten Eninen durch Sonogashira‐Kupplungen und verwandte Alkinylierungen

“…[34] Capretta et al zeigten, dass Trialkylphosphan-Phosphorinane ebenfalls als Liganden für die Sonogashira-Reaktion von Arylbromiden geeignet sind (Schema 11). [35] Die Reaktionen wurden bei Raumtemperatur in Dioxan mit HNiPr 2 als Base und CuI als Cokatalysator ausgeführt.…”

trans-Dichloro-bis(benzonitrile)palladium(II): A Versatile Reagent in Organic Synthesis

“…In addition, optimization revealed that Pd(PhCN) 2 Cl 2 was the best palladium source for these couplings. 12 ArCOCl + Ph …”