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Biocatalytic Atroposelective Synthesis of Axially Chiral <i>N</i>-Arylindoles via Dynamic Kinetic Resolution

Patricia Rodríguez‐Salamanca, Gonzalo de Gonzalo, José A. Carmona, Joaquín López‐Serrano, Javier Iglesias‐Sigüenza, Rosario Fernández, José M. Lassaletta, Valentı́n Hornillos

2022ACS Catalysis59 citationsDOIOpen Access PDF

Abstract

A highly enantioselective biocatalytic dynamic kinetic resolution (DKR) of configurationally labile N-arylindole aldehydes is described. The DKR proceeds by atroposelective bioreduction of the carbonyl group catalyzed by commercial ketoreductases (KREDs), thus affording the corresponding axially chiral N-arylindole aminoalcohols, with excellent conversions and optical purities. The strategy relies on the racemization of the stereogenic axis that takes place thanks to a transient Lewis pair interaction between the NMe2 and the aldehyde groups. This protocol features a broad substrate scope under very mild conditions.

Topics & Concepts

Kinetic resolutionRacemizationChemistryStereocenterEnantioselective synthesisBiocatalysisAldehydeCatalysisSubstrate (aquarium)UmpolungCombinatorial chemistryOrganic chemistryStereochemistryReaction mechanismGeologyNucleophileOceanographyAxial and Atropisomeric Chirality SynthesisMolecular spectroscopy and chiralitySphingolipid Metabolism and Signaling
Biocatalytic Atroposelective Synthesis of Axially Chiral <i>N</i>-Arylindoles via Dynamic Kinetic Resolution | Litcius