Energy-transfer photocatalysis for Minisci C-H (amino)alkylation of heteroarenes using oxime esters as dual-role reagents

• Published in: ORGANIC CHEMISTRY FRONTIERS Vol. 11; no. 18; pp. 5122 - 5129
• Main Authors: Xu, Jun, Zhang, Yuru, Xu, Ruiyuan, Wang, Yuxin, Shen, Jiabin, Li, Wanmei
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 10.09.2024; Royal Society of Chemistry
• Subjects: Alkenes; Alkylation; Amino acids; Carboxylic acids; Chemistry; Chemistry, Organic; Energy transfer; Esters; Oxidants; Oxidizing agents; Oxime esters; Photocatalysis; Physical Sciences; Reagents; Science & Technology; BORONIC ACIDS; BOND-DISSOCIATION ENERGIES; ALKYLATION; ARYLATION; CASCADE; RADICALS; MOLECULAR-OXYGEN
• ISSN: 2052-4129; 2052-4110; 2052-4110
• DOI: 10.1039/d4qo00836g

Utilization of oxime esters as bifunctional reagents in energy-transfer photocatalysis has received considerable attention. However, the reaction type is so far limited to the difunctionalization of alkenes. To confront this limitation and enrich Minisci-type chemistry, herein we have developed a green and practical protocol for Minisci C-H (amino)alkylation of heteroarenes employing diverse oxime esters (from carboxylic acids) as (amino)alkylating reagents. The key to success of this Minisci reaction is that oxime esters play a dual role of (amino)alkylating reagents and oxidants. In addition, the useful approach not only tolerates a wide range of heteroarenes but also features a broad compatibility with different alkyl radicals, including primary-, secondary-, and tertiary-carbon species. Moreover, the practicability of this method is additionally boosted by the functionalization of various amino acids and approved carboxyl-containing drugs. This methodology not only provides a practical strategy for direct decarboxylative C-H (amino)alkylation of heteroarenes, but also broadens the reaction types for the mechanism involving photocatalyzed energy transfer. This study demonstrates a strategy involving photoinduced energy transfer for decarboxylative Minisci C-H (amino)alkylation of heteroarenes employing diverse oxime esters (from carboxylic acids) as (amino)alkylating reagents.