Rhodium-catalyzed enantioselective intramolecular C-H silylation for the syntheses of planar-chiral metallocene siloles

Angew Chem Int Ed Engl. 2015 Jun 1;54(23):6918-21. doi: 10.1002/anie.201502548. Epub 2015 Apr 23.

Abstract

Reported herein is the rhodium-catalyzed enantioselective C-H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)-TMS-Segphos, the reactions took place under very mild conditions to afford metallocene-fused siloles in good to excellent yields and with ee values of up to 97%. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C-H silylations.

Keywords: chirality; ligand effects; metallocenes; rhodium; silicon.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Ferric Compounds / chemistry*
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry*
  • Rhodium / chemistry*
  • Silanes / chemistry*
  • Stereoisomerism

Substances

  • Ferric Compounds
  • Organometallic Compounds
  • Silanes
  • silole
  • Rhodium