Decarboxylative oxidation-enabled consecutive C-C bond cleavage

• Published in: Nature communications Vol. 13; no. 1; p. 7061
• Main Authors: Li, Ruining, Dong, Ya, Khan, Shah Nawaz, Zaman, Muhammad Kashif, Zhou, Junliang, Miao, Pannan, Hu, Lifu, Sun, Zhankui
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group 18.11.2022; Nature Publishing Group UK; Nature Portfolio
• Subjects: Carboxylic acids; Catalysis; Chemical bonds; Chemical synthesis; Cleavage; Copper; Covalent bonds; Ductile-brittle transition; Organic chemistry; Oxidation; Oxidation process; Photoredox catalysis; Radicals; Substrates; Transition metals
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-34829-x

Abstract The selective cleavage of C-C bonds is of fundamental interest because it provides an alternative approach to traditional chemical synthesis, which is focused primarily on building up molecular complexity. However, current C-C cleavage methods provide only limited opportunities. For example, selective C(sp 3 )-C(sp 3 ) bond cleavage generally relies on the use of transition-metal to open strained ring systems or iminyl and alkoxy radicals to induce β-fragmentation. Here we show that by merging photoredox catalysis with copper catalysis, we are able to employ α-trisubstituted carboxylic acids as substrates and achieve consecutive C-C bond cleavage, resulting in the scission of the inert β-CH 2 group. The key transformation relies on the decarboxylative oxidation process, which could selectively generate in-situ formed alkoxy radicals and trigger consecutive C-C bond cleavage. This complicated yet interesting reaction might help the development of other methods for inert C(sp 3 )-C(sp 3 ) bond cleavage.