DFT-Guided Photocatalytic C5-Selective Hydrodechlorination of 4,5-Dichloropyridazinones
Zi-Han Zhuang1, Qian Yan1, Zi-Qing Yu1
1Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation & Hunan Provincial Key Laboratory of CytoChemistry, School of Chemistry and Pharmaceutical Engineering, Changsha University of Science and Technology, Changsha, 410114, China.
Abstract:
A visible-light photocatalytic method for the C5-selective monohydrodechlorination of 4,5-dichloropyridazinones is described. Using Eosin Y-Na2 and DIPEA, the reaction proceeds under mild conditions and tolerates a wide range of N2 substituents and functional groups. Mechanistic studies support a single-electron transfer pathway involving a C5-centered radical, with DFT calculations revealing that the inherently weaker C5-Cl bond (87.1 vs 89.1 kcal/mol) accounts for the selectivity, while kinetic control from neutral DIPEA dictates the reaction outcome.
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