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Autocatalytic Carbonyl Arylation through In Situ Release of Aryl Nucleophiles from N ‐Aryl‐ N ′‐Silyldiazenes
Author(s) -
Chauvier Clément,
Finck Lucie,
Irran Elisabeth,
Oestreich Martin
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201916004
Subject(s) - nucleophile , chemistry , electrophile , aryl , lewis acids and bases , catalysis , silylation , alkali metal , medicinal chemistry , autocatalysis , organic chemistry , alkyl
A method for the catalytic generation of functionalized aryl alkali metals is reported. These highly reactive intermediates are liberated from silyl‐protected aryl‐substituted diazenes by the action of Lewis basic alkali metal silanolates, resulting in desilylation and loss of N 2 . Catalytic quantities of these Lewis bases initiate the transfer of the aryl nucleophile from the diazene to carbonyl and carboxyl compounds with superb functional‐group tolerance. The aryl alkali metal can be decorated with electrophilic substituents such as methoxycarbonyl or cyano as well as halogen groups. The synthesis of a previously unknown cyclophane‐like [4]arene macrocycle from a 1,3‐bisdiazene combined with a 1,4‐dialdehyde underlines the potential of the approach.