Carbon-carbon triple bond cleavage and reconstitution to achieve aryl amidation using nitrous acid esters.

Wang, Zi-Ying; Wang, Shoujun; Dai, Nan-Nan; Xiao, Yao; Zhou, Yu; Tian, Wen-Chan; Sun, Dongru; Li, Qiang et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

C-C bond cleavage and recombination provide an efficient strategy for the modification and reconstruction of molecule structures. Herein, we present a method for achieving amidation of aryl C(sp<sup>2</sup>)-H bond through the cleavage and recombination of C-C triple bond with the involvement of nitrous acid esters. This method marks the instance of precise and controlled stepwise cleavage of C-C triple bond, offering a fresh perspective for the cleavage of such bonds. Nitrous acid ester serves as both a radical source and a hydrogen atom transfer (HAT) reagent to functionalize and utilize the two carbon atoms of the C-C triple bond. The alkoxy radical captures the hydrogen atom from the aryl C(sp<sup>2</sup>)-H bond or N-hydroxyl to induce the 1,3-oxygen radical migration, which is crucial for the subsequent cleavage of the C-C bond.