Lithium‐Aluminate‐Catalyzed Hydrophosphination Applications. Issue 35 (25th July 2019)

• Record Type: Journal Article
• Authors: Pollard, Victoria A.; Young, Allan; McLellan, Ross; Kennedy, Alan R.; Tuttle, Tell; Mulvey, Robert E.
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 35(2019)
• Page Start: 12291
• Page End: 12296
• Publication Date: 2019-07-25
• Subjects: aluminate -- homogeneous catalysis -- hydrophosphination -- lithium -- phosphines; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201906807
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Synthesized, isolated, and characterized by X‐ray crystallography and NMR spectroscopic studies, lithium phosphidoaluminate iBu3 AlPPh2 Li(THF)3 has been tested as a catalyst for hydrophosphination of alkynes, alkenes, and carbodiimides. Based on the collective evidence of stoichiometric reactions, NMR monitoring studies, kinetic analysis, and DFT calculations, a mechanism involving deprotonation, alkyne insertion, and protonolysis is proposed for the [iBu3 AlHLi]2 aluminate catalyzed hydrophosphination of alkynes with diphenylphosphine. This study enhances further the development of transition‐metal‐free, atom‐economical homogeneous catalysis using common sustainable main‐group metals. Abstract : Alluring aluminum : Catalytic hydrophosphination of unsaturated organic substrates is usually associated with transition metals, but aluminum is now found to be an attractive catalytic partner.