Competing Pathways in O-Arylations with Diaryliodonium Salts: Mechanistic Insights
Elin Stridfeldt1, Erik Lindstedt1, Marcus Reitti1
1Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91, Stockholm, Sweden.
Abstract:
A mechanistic study of arylations of aliphatic alcohols and hydroxide with diaryliodonium salts, to give alkyl aryl ethers and diaryl ethers, has been performed using experimental techniques and DFT calculations. Aryne intermediates have been trapped, and additives to avoid by-product formation originating from arynes have been found. An alcohol oxidation pathway was observed in parallel to arylation; this is suggested to proceed by an intramolecular mechanism. Product formation pathways via ligand coupling and arynes have been compared, and 4-coordinated transition states were found to be favored in reactions with alcohols. Furthermore, a novel, direct nucleophilic substitution pathway has been identified in reactions with electron-deficient diaryliodonium salts.
More Related Videos
09:54Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes
Published on: September 12, 2018
09:58Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
Related Concept Videos
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
