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Concepts for stereoselective acrylate insertion.

Boris Neuwald1, Lucia Caporaso, Luigi Cavallo

  • 1Chair of Chemical Materials Science, Department of Chemistry, University of Konstanz, 78464 Konstanz, Germany.

Journal of the American Chemical Society
|December 22, 2012
PubMed
Summary
This summary is machine-generated.

This study synthesized palladium complexes with phosphinesulfonato ligands, revealing that ligand flexibility and steric bulk impact stereocontrol in methyl acrylate insertion. Asymmetric ligands enhance initial stereoselectivity, but consecutive insertions show diminished control due to competing stereocontrol factors.

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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Ligand Design

Background:

  • Palladium complexes with phosphinesulfonato ligands are explored for catalytic applications.
  • Understanding ligand dynamics and steric effects is crucial for controlling catalytic outcomes.
  • Stereocontrol in insertion reactions remains a significant challenge in catalysis.

Purpose of the Study:

  • To synthesize and characterize novel phosphinesulfonato ligands and their palladium complexes.
  • To investigate the influence of ligand structure, particularly steric bulk and symmetry, on molecular motion and dynamics.
  • To elucidate the stereoselectivity of methyl acrylate insertion into the palladium-methyl bond and understand the factors governing this process.

Main Methods:

  • Synthesis of various symmetric and asymmetric phosphinesulfonato ligands and palladium complexes.
  • Variable temperature NMR studies and line shape analysis to probe molecular motions and determine energy barriers.
  • Investigation of methyl acrylate insertion stereoselectivity using in situ NMR and Density Functional Theory (DFT) calculations.

Main Results:

  • Palladium complexes with phosphinesulfonato ligands were successfully synthesized.
  • Aryl rotation in ligands and complexes exhibited high energy barriers (44-64 kJ/mol), with steric bulk increasing these barriers.
  • Ligand substitution pattern significantly affected the first methyl acrylate insertion, achieving stereoselectivity up to 6:1 with asymmetric ligands, while consecutive insertions showed diminished stereoselectivity.

Conclusions:

  • Ligand flexibility and steric bulk are critical factors influencing catalytic performance, with increased bulk hindering insertion rates and regioselectivity.
  • Asymmetric phosphinesulfonato ligands can provide high stereoselectivity in the first insertion step.
  • The diminished stereoselectivity in consecutive insertions is attributed to competing enantiomorphic and chain-end stereocontrol mechanisms, necessitating further conceptual development for improved control.