Lithium-aluminate-catalyzed hydrophosphination applications

Pollard, Victoria A. and Young, Allan and McLellan, Ross and Kennedy, Alan R. and Tuttle, Tell and Mulvey, Robert E. (2019) Lithium-aluminate-catalyzed hydrophosphination applications. Angewandte Chemie International Edition, 58 (35). pp. 12291-12296. ISSN 1433-7851 (

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Synthesized, isolated, and characterized by X-ray crystallography and NMR spectroscopic studies, lithium phosphidoaluminate iBu3AlPPh2Li(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 [iBu3AlHLi]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.