Halogen Atom Participation in Guiding the Stereochemical Outcomes of Acetal Substitution Reactions

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 Aug 18

PMID 35980341

Authors

Krystyna M Demkiw

Wouter A Remmerswaal

Thomas Hansen

Gijsbert A van der Marel

Jeroen D C Codee

K A Woerpel

Affiliations

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Abstract

Acetal substitution reactions of α-halogenated five- and six-membered rings can be highly stereoselective. Erosion of stereoselectivity occurs as nucleophilicity increases, which is consistent with additions to a halogen-stabilized oxocarbenium ion, not a three-membered-ring halonium ion. Computational investigations confirmed that the open-form oxocarbenium ions are the reactive intermediates involved. Kinetic studies suggest that hyperconjugative effects and through-space electrostatic interactions can both contribute to the stabilization of halogen-substituted oxocarbenium ions.

Citing Articles

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Halogen Atom Participation in Guiding the Stereochemical Outcomes of Acetal Substitution Reactions.

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PMID: 35980341 PMC: 9561118. DOI: 10.1002/anie.202209401.

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