Chalcogen‐Bonding‐Enabled, Light‐Driven Decarboxylative Oxygenation of Amino Acid Derivatives and Short Peptides using O2

Abstract

Here we report a photocatalytic method for the decarboxylative oxygenation of amino acid derivatives and short peptides using dioxygen as a green oxidant. A reverse catalytic strategy utilizing Lewis basic diphenyl diselenide as a Lewis acid catalyst to activate carboxylic acid via chalcogen bonding interaction is the key to this work. This synthetic method is tolerant of functionalities present in both natural and non‐proteinogenic amino acids, enabling the efficient synthesis of C‐terminal amides or imides. Mechanistic studies suggest there is a dual noncovalent interaction between diphenyl diselenide and carboxylic acid, which allows radical decarboxylation through photoinduced intermolecular electron transfer. This new activation mode of carboxylic acids will add a new dimension to classical decarboxylative reactions.