Abstract
Given the abundance and the ready availability of anilines, the selective insertion of atoms into the aryl carbon–nitrogen bonds will be an appealing route for the synthesis of nitrogen-containing aromatic molecules. However, because aryl carbon–nitrogen bonds are particularly inert, anilines are normally activated by conversion to more reactive intermediates such as aryldiazonium salts to achieve functionalization of the aryl carbon–nitrogen bonds, but the nitrogen atom is usually not incorporated into products, instead being discarded. The selective insertion of groups into aryl carbon–nitrogen bonds remains an elusive challenge and an unmet need in reaction design. Here we show an aromaticity destruction-reconstruction process that selectively inserts a trimethylenemethane (TMM) group into the aromatic carbon–nitrogen bond of anilines concomitant with a benzylic carbon–hydrogen bond functionalization. This process provides a transformative mode for anilines, and the insertion products are versatile precursor to various nitrogen-containing aromatic molecules through simple conversions.
Highlights
Given the abundance and the ready availability of anilines and their derivatives, the selective insertion of atoms into the aryl carbon–nitrogen bonds will be an appealing route for the synthesis of nitrogencontaining aromatic molecules
These elegant methods have enabled the synthesis of a variety of functionalized aromatic molecules using anilines as the aryl source, the nitrogen atom in substrates is usually not incorporated into products, instead it is being discarded
In connection with our recent research on the functionalization of the aryl carbon–nitrogen bonds by using the dearomatization strategy[50], we investigated the reaction of anilines with palladium–TMM (Pd–TMM) complexes under oxidative dearomatization conditions
Summary
Given the abundance and the ready availability of anilines, the selective insertion of atoms into the aryl carbon–nitrogen bonds will be an appealing route for the synthesis of nitrogencontaining aromatic molecules. Transition-metal-catalyzed group insertion into unreactive aryl chemical bonds such as carbon–carbon[1,2,3], carbon–cyanide[4,5,6], or carbon–halogen[7,8,9] bonds has drawn particular attention since aromatic molecular complexity can be rapidly built without the generation of stoichiometric amounts of waste products (Fig. 1a) In this context, given the abundance and the ready availability of anilines and their derivatives, the selective insertion of atoms into the aryl carbon–nitrogen bonds will be an appealing route for the synthesis of nitrogencontaining aromatic molecules. This group insertion process provides a transformative mode for anilines and the TMM insertion products are versatile precursors to a variety of nitrogencontaining aromatic molecules through simple conversions
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