Herein, we report an intriguing cascade strategy for synthesizing optically active fused pyrazolidines featuring three contiguous stereogenic centers. The formyl-tethered enones are templates for the developed umpolung reactivity, showcasing diverse substrate adaptability with various arylhydrazines. The chiral phosphoric acid catalyst offers stereochemical guidance, forming the fused pyrazolidines with commendable to excellent stereoselectivities. Additionally, the scalability, postsynthetic transformations, and instability of unacylated pyrazolidines have been successfully demonstrated.
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Asymmetric Synthesis of Optically Active Pyrazolidines or Pyrazoline Derivatives via Ni(II)-Bipyridine-,'-dioxide Complexes.
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School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003, China.
Easily obtainable and efficient chiral -symmetric bipyridine-,'-dioxide ligands with Ni(OTf) were developed for application in catalyzing [3 + 2] cycloaddition reactions to synthesize optically active fused pyrazolidines or pyrazoline derivatives featuring three contiguous stereogenic centers by employing azomethine imines and α,β-unsaturated 2-acyl imidazoles, affording the corresponding adducts with the opposite configuration compared to previous synthetic products in 80-98% yields with 28-99% ee and >20:1 dr. In addition, subsequent amplification experiments and derivative transformations of the product further demonstrated the efficient catalytic performance of the catalyst Ni(II)-bipyridine-,'-dioxide complexes and the practicality of this synthesis methodology.
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Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Bhopal By-pass Road, Bhauri, Bhopal 462066, India.
Herein, we report an intriguing cascade strategy for synthesizing optically active fused pyrazolidines featuring three contiguous stereogenic centers. The formyl-tethered enones are templates for the developed umpolung reactivity, showcasing diverse substrate adaptability with various arylhydrazines. The chiral phosphoric acid catalyst offers stereochemical guidance, forming the fused pyrazolidines with commendable to excellent stereoselectivities.
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