Tertiary phosphines: preparation and reactivity

Coinage Metal Complexes of Bis(quinoline‐2‐ylmethyl)phenylphosphine‐Simple Reactions Can Lead to Unprecedented Results

“…This versatile coordination behavior is very beneficial and needed in catalysis, for the preparation of MOFs or even luminescent materials. [1][2][3][4][5][6][7][8][9][10][11][12][13] Hemilabile tertiary phosphines are preferably used due to their outstanding flexibility which can be modified by changing the substituents accordingly. The modification of the substituents can result in the adaptation of their steric and electronic properties, their bite angle and solubility, and even chiral phosphine ligands can be formed.…”

Nickel-Catalyzed Diversification of Phosphine Ligands by Formal Substitution at Phosphorus

“…[2,3] A significant benefit of phosphines is that the ligand's electronic and steric properties can be tuned with precision by varying the substituents on the phosphorus center. Taking advantage of a versatile toolbox of synthetic methods to access phosphines, [4] many powerful phosphine ligand architectures have been developed. [5][6][7][8][9][10][11] Phosphines have also been employed in numerous other applications such as organocatalysis, [12,13] frustrated Lewis pair catalysis, [14,15] or material sciences.…”

“…Traditionally, phosphine ligands are prepared by de novo synthetic approaches such as nucleophilic substitution reactions of halophosphine substrates with organometallic reagents. [4] Alternative strategies include the reduction of phosphine oxides [18][19][20][21] or reactions of hydrophosphines such as the hydrophosphination of unsaturated systems, [22][23][24] cross-coupling with aryl halides, [25,26] or substitution reactions with electrophiles in the presence of base. [4,27] Combined, these methods allow access to a plethora of diverse phosphine architectures.…”

“…[4] Alternative strategies include the reduction of phosphine oxides [18][19][20][21] or reactions of hydrophosphines such as the hydrophosphination of unsaturated systems, [22][23][24] cross-coupling with aryl halides, [25,26] or substitution reactions with electrophiles in the presence of base. [4,27] Combined, these methods allow access to a plethora of diverse phosphine architectures. However, they typically require multi-step procedures involving highly toxic or pyrophoric reagents and air-sensitive intermediates.…”

“…With these results in hand, we investigated the scope of the reaction. Phosphonium salts containing different alkyl groups were prepared by alkylation of phosphines in good to high yields using standard methods [4] (see SI) and then subjected to the dearylation reaction (Scheme 2). For ease of purification, the phosphine products were typically isolated after in situ conversion to the borane adducts.…”