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Enantioselective Synthesis of Dihydropyrazoles by Palladium/Xu‐Phos‐Catalyzed Alleneamination of β,γ‐Unsaturated Hydrazones with Propargylic Acetates

Shuting Zhang, Shuaijie Wu, Qiang Wang, Shiji Xu, Ying Han, Chao‐Guo Yan, Junliang Zhang, Lei Wang

2023Angewandte Chemie International Edition30 citationsDOI

Abstract

The palladium-catalyzed asymmetric carboamination reaction is one of the most significant transformations in organic chemistry. Herein, we report the first palladium-catalyzed asymmetric alleneamination of β,γ-unsaturated hydrazones with propargylic acetates. This protocol enables the efficient installation of various multisubstituted allene groups onto dihydropyrazoles in good yields with excellent enantioselectivities. The chiral sulfinamide phosphine ligand Xu-5 exhibits highly efficient stereoselective control in this protocol. The salient features of this reaction include the readily available starting materials, a broad substrate scope, an easy scale-up, mild reaction conditions and versatile transformations.

Topics & Concepts

ChemistryEnantioselective synthesisAllenePalladiumCatalysisCombinatorial chemistryPhosphineSubstrate (aquarium)Ligand (biochemistry)StereoselectivityOrganic chemistryBiochemistryGeologyOceanographyReceptorCatalytic C–H Functionalization MethodsSulfur-Based Synthesis TechniquesCatalytic Alkyne Reactions
Enantioselective Synthesis of Dihydropyrazoles by Palladium/Xu‐Phos‐Catalyzed Alleneamination of β,γ‐Unsaturated Hydrazones with Propargylic Acetates | Litcius