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Free, publicly-accessible full text available February 12, 2026
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Abstract Transition metal‐catalyzed, non‐enzymatic nitrene transfer (NT) reactions to selectively transform C−H and C=C bonds to new C−N bonds are a powerful strategy to streamline the preparation of valuable amine building blocks. However, many catalysts for these reactions use environmentally unfriendly solvents that include dichloromethane, chloroform, 1,2‐dichloroethane and benzene. We developed a high‐throughput experimentation (HTE) protocol for heterogeneous NT reaction mixtures to enable rapid screening of a broad range of solvents for this chemistry. Coupled with the American Chemical Society Pharmaceutical Roundtable (ACSPR) solvent tool, we identified several attractive replacements for chlorinated solvents. Selected catalysts for NT were compared and contrasted using our HTE protocol, including silver supported byN‐dentate ligands, dinuclear Rh complexes and Fe/Mn phthalocyanine catalysts.more » « less
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