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

[img]
Preview
Text (Mulvey-etal-ACIE-2019-lithium-aluminate-catalyzed-hydrophosphination-applications)
Mulvey_etal_ACIE_2019_lithium_aluminate_catalyzed_hydrophosphination_applications.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo

Download (1MB)| Preview

    Abstract

    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.