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Autocatalytic Carbonyl Arylation through In Situ Release of Aryl Nucleophiles from NâArylâNâ˛âSilyldiazenes
A method for the catalytic generation of functionalized aryl alkali metals is reported. These highly reactive intermediates are liberated from silylâprotected arylâsubstituted 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 functionalâgroup 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 cyclophaneâlike [4]arene macrocycle from a 1,3âbisdiazene combined with a 1,4âdialdehyde underlines the potential of the approach.TU Berlin, Open-Access-Mittel â 202