Rujuan Li, Renqin Zhan, Yatao Lang, Chao-Jun Li and Huiying Zeng
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Intermolecular C–C/C–N σ-bond metathesis enabled by visible light†
Transition-metal-catalyzed double/triple bond metathesis reactions have been well-established due to the ability of transition-metal catalysts to readily interact with π bonds, facilitating the progression of the entire reaction. However, activating σ-bonds to induce σ-bond metathesis is more challenging due to the absence of π bonds and the high bond energy of σ bonds. In this study, we present a novel photo-induced approach that does not rely on transition metals or photosensitizers to drive C–C and C–N σ-bond metathesis reactions. This method enables the cross-coupling of tertiary amines with α-diketones via C–C and C–N single bonds cleavage and recombination. Notably, our protocol exhibits good compatibility with various functional groups in the absence of transition metals and external photosensitizers, resulting in the formation of aryl alkyl ketones and aromatic amides in good to high yields. To gain insights into the mechanism of this pathway, we conducted controlled experiments, intermediate trapping experiments, and DFT (Density Functional Theory) calculations. This comprehensive approach allowed us to elucidate the detailed mechanism underlying this transformative reaction.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.