New Approaches to Nitrogen-Containing Compounds - Organocatalyzed Amination and Photoinduced Aminoalkylation

Date

2023-04-25

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Abstract

Nitrogen-containing compounds, including basic amines and N-aryl azoles, are essential building blocks to construct functional molecules, including transition-metal catalysis ligands and pharmaceutical compounds. Although the methodology for these compounds has been investigated for a few decades, significant limitations and drawbacks remain. Therefore, new synthetic pathways toward nitrogen-containing compounds are still in high demand. Two new approaches to nitrogen-containing compounds have been developed. Firstly, we achieved the transition-metal-free condensation between phenols and sulfones. The reaction furnished the N-aryl products in high yield through a nucleophilic aromatic substitution process. A plausible mechanism was proposed with the characterization of key intermediates. Secondly, we reported an intermolecular imine alkylation involving C-H activation and triplet photochemistry. The transformation was transition-metal-free, with no protecting or leaving group, under mild conditions, and delivered the primary amines directly. The scope of this reaction was broad, and most substrates gave a high yield. Besides that, the protocol was successfully operated on the inactive sp3 C-H bonds and tolerated oxidable, coordinating, and protic functional groups. Moreover, a detailed triplet excited-state mechanism for this reaction was proposed and fully characterized by mechanistic experiments.

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Keywords

Amine, Azole, Organocatalysis, Photochemical

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