DFT/MM study on copper-catalyzed cyclopropanation - Enantioselectivity with no enthalpy barrier

Galí Drudis-Sole, Feliu Maseras, Agustí Lledós, Adelina Vallribera, Marcial Moreno-Mañas

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19 Citations (Scopus)

Abstract

The enantioselectivity in the reaction of [Cu(adam-box)-(CHCO 2Me)] {adam-box = 2,2′-isopropylidenebis[(4R)-(1-adamantyl)-2- oxazoline]} with Ph2C=CH2 was analyzed computationally by ONIOM(B3LYP:UFF) calculations. The lack of transition states in the potential-energy surface precludes the use of conventional approaches and requires the definition of reaction paths in an approximate Gibbs free-energy surface. The procedure is time consuming and intrinsically less accurate than the usual approaches based on enthalpic energy surfaces, but it produces results in reasonable agreement with experiment, which furthermore allow identification of the key interactions responsible for chiral discrimination. © Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
Original languageEnglish
Pages (from-to)5614-5621
JournalEuropean Journal of Organic Chemistry
Issue number33
DOIs
Publication statusPublished - 1 Nov 2008

Keywords

  • Carbene ligands
  • Copper
  • Cyclopropanation
  • Density functional calculations
  • Enantioselectivity

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