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Updated: Jun 19, 2026

Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines
Published on: January 3, 2018
Sulfonyl-PYBOX/ErCl3 complex enable highly enantioselective synthesis of α,α-dialkyl and α-alkyl-α-aryl
Yi Gong1, Zheng Zhang1, Qiang Cao1
1State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China.
Abstract:
We report the highly enantioselective nucleophilic addition reaction of simple ketone-derived hydrazones. Accordingly, a ErCl₃-catalyzed cyanation of both aliphatic and aryl ketone hydrazones is achieved for the facile access of Cα-tetrasubstituted α-hydrazino nitriles in up to 96% ee, by using the sterically confined pyridinebisoxazoline (PYBOX) ligand featuring a sulfonyl group at the pyridine C4 position. This method enables the shortest catalytic enantioselective total synthesis of L-carbidopa, a drug that could treat the symptoms of Parkinson's disease, with 82% overall yield in four steps. These adducts are valuable synthons to various α-tertiary hydrazines and related azacycles that are interesting targets for medicinal studies and pesticide research. From our biological analysis, a chiral α-hydrazino nitrile with good insecticidal activity against Aphis gossypii (LC50 = 15.11 mg∙L-1) was identified, rivaling commercial insecticides.
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