Comparing the enantioselective power of steric and electrostatic effects in transition-metal-catalyzed asymmetric synthesis

Albert Poater, Francesco Ragone, Ronaldo Mariz, Reto Dorta*, Luigi Cavallo

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

139 Scopus citations

Abstract

The current approach to improve and tune the enantioselective performances of transition-metal catalysts for asymmetric synthesis is mostly focused to modifications of the steric properties of the ancillary ligands of the active metal. Nevertheless, it is also known that electrostatic effects can have a remarkable role to promote selectivity in asymmetric synthesis. Using the Rh-catalyzed asymmetric 1,4-addition of phenylboronic acid to 2-cyclohexenone leading to chiral 3-phenylcyclohexanone as an example, we could show that high enantioselectivity can be indeed achieved using catalysts essentially based either on steric or electrostatic effects as the main source of enantioselective induction. In this contribution we suggest that the analysis of the surface of interaction between the catalyst and the substrate could be a useful tool to quantify the power of steric and electrostatic effects of catalysts. Steric versus electronic: Analysis of two prototype Rh catalysts show that high enantioselectivity in asymmetric synthesis can be achieved using either steric or electrostatic effects. Topographic maps of the interaction surface between the catalyst and the substrate are proposed as a tool to quantify these effects.

Original languageEnglish (US)
Pages (from-to)14348-14353
Number of pages6
JournalChemistry - A European Journal
Volume16
Issue number48
DOIs
StatePublished - Dec 27 2010

Keywords

  • asymmetric catalysis
  • enantioselectivity
  • homogeneous catalysis
  • rhodium

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Fingerprint

Dive into the research topics of 'Comparing the enantioselective power of steric and electrostatic effects in transition-metal-catalyzed asymmetric synthesis'. Together they form a unique fingerprint.

Cite this