Catalyst optimisation for asymmetric synthesis by ligand chirality element addition - a perspective on stereochemical cooperativity

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Abstract

The concept of matched and mismatched stereochemical pairings has been utilised extensively in organic synthesis, with the cooperativity resulting from the former enabling many reactions to proceed with high stereoselectivity. This approach was first developed to improve the diastereoselectivity of a reaction by matching the configuration of an enantiopure reagent or catalyst with the configuration of an enantiopure substrate. It has been extended to the asymmetric transformation of prochiral substrates controlled by reagents and catalysts containing two or more stereogenic centres. Matched and mismatched pairings may again be identified, with the former resulting in higher product enantioselectivity. This Minireview examines stereochemical pairings within catalysts generated from the combination of a metal with an enantiopure ligand; specifically examples where the ligand diastereoisomers examined for cooperativity are formally the result of the addition of a chiral element to an existing enantiopure ligand. Comparison of all three ligands in each of the fifty-six examples examined reveals that in the majority of cases the added element of chirality increases and decreases the enantioselectivity with respect to the parent ligand. The iterative application of this effect offers a potentially powerful method for catalyst optimisation for use in asymmetric synthesis.
Original languageEnglish
Pages (from-to)11460–11478
Number of pages19
JournalChemistry - A European Journal
Volume23
Issue number48
Early online date18 Apr 2017
DOIs
Publication statusPublished - 25 Aug 2017

Keywords

  • asymmetric catalysis
  • ligand design
  • chelates
  • matched and mismatched
  • stereochemical cooperativity

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