C2-symmetric chiral disulfoxide ligands in rhodium-catalyzed 1,4-addition: From ligand synthesis to the enantioselection pathway

Ronaldo Mariz, Albert Poater, Michele Gatti, Emma Drinkel, Justus J. Bürgi, Xinjun Luan, Sascha Blumentritt, Anthony Linden, Luigi Cavallo*, Reto Dorta

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

50 Scopus citations

Abstract

A family of chiral C2-symmetric disulfoxide ligands possessing biaryl atropisomeric backbones has been synthesized by using the Andersen methodology. Complete characterization includes X-ray crystallographic studies of all ligands and some of their rhodium complexes. Their synthesis, optical purity, electronic properties, and catalytic behavior in the prototypical rhodium-catalyzed 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one are presented through an in depth study of this ligand class. Density functional theory calculations on the step of the catalytic cycle that determines the enantioselectivity are presented and reinforce the first hypothetical explanations for the high levels of asymmetric induction observed.

Original languageEnglish (US)
Pages (from-to)14335-14347
Number of pages13
JournalChemistry - A European Journal
Volume16
Issue number48
DOIs
StatePublished - Dec 27 2010

Keywords

  • asymmetric catalysis
  • chiral auxiliaries
  • conjugate addition
  • enantioselectivity
  • sulfoxides

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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