Formal group insertion into aryl C‒N bonds through an aromaticity destruction-reconstruction process

Area of Science:

• Organic Chemistry
• Synthetic Chemistry

Background:

• Anilines are abundant precursors for nitrogen-containing aromatic molecules.
• Aryl carbon-nitrogen bonds in anilines are typically inert and difficult to functionalize directly.
• Existing methods often discard the aniline nitrogen atom during functionalization.

Purpose of the Study:

• To develop a novel method for the selective functionalization of aryl carbon-nitrogen bonds in anilines.
• To achieve the direct insertion of a trimethylenemethane (TMM) group into the C-N bond of anilines.
• To enable the synthesis of versatile nitrogen-containing aromatic compounds.

Main Methods:

• An aromaticity destruction-reconstruction strategy was employed.
• The process selectively targets the aryl carbon-nitrogen bond of anilines.
• Simultaneous functionalization of a benzylic carbon-hydrogen bond was achieved.

Main Results:

• Successful selective insertion of a trimethylenemethane (TMM) group into the aryl carbon-nitrogen bond of anilines.
• Demonstration of concomitant benzylic carbon-hydrogen bond functionalization.
• The resulting products serve as versatile precursors for various nitrogen-containing aromatic molecules.

Conclusions:

• The developed method offers a transformative approach for aniline functionalization.
• This strategy overcomes the inertness of aryl carbon-nitrogen bonds.
• The process provides a new pathway to synthesize diverse nitrogen-containing aromatic compounds.