Autocatalytic Carbonyl Arylation through In Situ Release of Aryl Nucleophiles from N-Aryl-N'-Silyldiazenes.

ABSTRACT: 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 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.

SUBMITTER: Chauvier C 

PROVIDER: S-EPMC7383908 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature