Electrophilic Phosphonium Cation-Mediated Phosphane Oxide Reduction Using Oxalyl Chloride and Hydrogen
The metal-free reduction of phosphane oxides with molecular hydrogen (H2) using oxalyl chloride as activating agent was achieved. Quantum-mechanical investigations support the heterolytic splitting of H2 by the in situ formed electrophilic phosphonium cation (EPC) and phosphane oxide and subsequent barrierless conversion to the phosphane and HCl. The reaction can also be catalyzed by the frustrated Lewis pair (FLP) consisting of B(2,6-F2C6H3)3 and 2,6-lutidine or phosphane oxide as Lewis base. This novel reduction was demonstrated for triaryl and diaryl phosphane oxides providing access to phosphanes in good to excellent yields (51–93 %).
Stepen, Arne J.,Bursch, Markus,Grimme, Stefan,Stephan, Douglas W.,Paradies, Jan
supporting information
p. 15253 - 15256
(2018/10/24)
A concise synthesis of a new xylyl-biaryl diphosphine ligand for asymmetric hydrogenation of ketones
A concise synthesis of a symmetrical biaryl diphosphine ligand bearing 3,5-dimethylphenyl substituents at phosphorus is described. The ruthenium catalysts [diphosphine RuCl2 diamine] containing the new ligand Xyl-TetraPHEMP were found to be as active and as selective as the state-of-the-art catalysts for homogeneous asymmetric ketone hydrogenation.
Henschke, Julian P.,Zanotti-Gerosa, Antonio,Moran, Paul,Harrison, Paul,Mullen, Brendan,Casy, Guy,Lennon, Ian C.
p. 4379 - 4383
(2007/10/03)
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