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Substrate‐Controlled Pd‐Catalyzed Divergent Decarboxylative Cycloaddition of Vinyloxazolidine‐2,4‐Diones with Azadienes for the Construction of Spirocycles and Medium‐Sized Heterocycles

Shi‐Ting Xie, Zhen‐Hua Wang, Yang Lei, Jian‐Qiang Zhao, Yong You, Yanping Zhang, Wei‐Cheng Yuan

2025Chinese Journal of Chemistry10 citationsDOIOpen Access PDF

Abstract

Comprehensive Summary Herein, we report a substrate‐controlled palladium‐catalyzed divergent decarboxylative cycloaddition of vinyloxazolidine‐2,4‐diones with azadienes. The reaction of benzofuran‐derived azadienes undergoes a decarboxylative (3+2) cycloaddition process to access spiro[benzofuran‐butyrolactam] derivatives in good yields with acceptable diastereoselectivities. In contrast, the reaction of benzothiophene‐based azadienes proceeds a decarboxylative (5+4) cycloaddition pathway to give benzothieno[1,2‐ d ]diazonin‐5‐ones in moderate to high yields. Gram‐scale synthesis and further transformations demonstrated the potential synthetic utility of the developed protocol.

Topics & Concepts

ChemistryCycloadditionCatalysisSubstrate (aquarium)Combinatorial chemistryOrganic chemistryGeologyOceanographyCatalytic C–H Functionalization MethodsCatalytic Alkyne ReactionsSynthesis and Characterization of Pyrroles