Autocatalytic Carbonyl Arylation through In Situ Release of Aryl Nucleophiles from N‐Aryl‐N′‐Silyldiazenes [article]

Clément Chauvier, Lucie Finck, Elisabeth Irran, Martin Oestreich, Technische Universität Berlin
2020
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 N2. 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
more » ... tal 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.
doi:10.14279/depositonce-10840 fatcat:syd6gwszqjg6loyzbapwtkpraq