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Decarboxylative oxidation-enabled consecutive C-C bond cleavage

Ruining Li, Ya Dong, Shah Nawaz Khan, Muhammad Kashif Zaman, Junliang Zhou, Pannan Miao, Lifu Hu, Zhankui Sun

2022Nature Communications29 citationsDOIOpen Access PDF

Abstract

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.

Topics & Concepts

Cleavage (geology)Bond cleavageChemistryBiochemistryBiologyCatalysisPaleontologyFracture (geology)Radical Photochemical ReactionsCatalytic C–H Functionalization MethodsOxidative Organic Chemistry Reactions
Decarboxylative oxidation-enabled consecutive C-C bond cleavage | Litcius