Atroposelective Silylation of 1,1′‐Biaryl‐2,6‐diols by a Chiral Counteranion Directed Desymmetrization Enhanced by a Subsequent Kinetic Resolution
Min Zhu, Hua‐Jie Jiang, Illia Sharanov, Elisabeth Irran, Martin Oestreich
Abstract
A desymmetrizing silylation of aromatic diols is reported. The previously unknown asymmetric silyl ether formation of phenol derivatives is achieved by applying List's counteranion directed silylation technique. A silylium-ion-like silicon electrophile generated from an allylic silane paired with an imidodiphosphorimidate (IDPi) enables enantioselective discrimination of achiral 1,1'-biaryl-2,6-diols. The enantioselectivity of that desymmetrization is further improved by a downstream kinetic resolution, converting the monosilylated minor enantiomer into the corresponding, again achiral bissilylated diol.
Topics & Concepts
DesymmetrizationSilylationKinetic resolutionChemistryEnantioselective synthesisElectrophileAllylic rearrangementEnantiomerSilaneDiolPhenolEtherResolution (logic)Organic chemistryCatalysisArtificial intelligenceComputer scienceAxial and Atropisomeric Chirality SynthesisMolecular spectroscopy and chiralityAsymmetric Synthesis and Catalysis