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Atroposelective Silylation of 1,1′‐Biaryl‐2,6‐diols by a Chiral Counteranion Directed Desymmetrization Enhanced by a Subsequent Kinetic Resolution

Zhu, Min; Jiang, Hua‐Jie; Sharanov, Illia; Irran, Elisabeth; Oestreich, Martin

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.
Published in: Angewandte Chemie International Edition, 10.1002/anie.202304475, Wiley-VCH