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A New Reaction Mode of 3-Halooxindoles: Acting as C–C–O Three-Atom Components for (3+3) Cycloaddition to Access Indolenine-Fused 2<i>H</i>-1,4-Oxathiines

Ting-Jia Sun, Xue-Song Peng, Wei Sun, Yanping Zhang, Xiaomin Ma, Jian‐Qiang Zhao, Zhen‐Hua Wang, Yong You, Ming‐Qiang Zhou, Jun‐Qing Yin, Wei‐Cheng Yuan

2023Organic Letters12 citationsDOI

Abstract

Herein, we report an unprecedented implementation of 3-halooxindoles as C–C–O three-atom components for (3+3) cycloaddition with pyridinium 1,4-zwitterionic thiolates, affording structurally diverse indolenine-fused 2 H -1,4-oxathiines in moderate to high yields. A combined experimental and computational mechanistic study suggests that the reaction proceeds through addition of a S conjugate to the o -azaxylylene intermediate, followed by O-Michael addition and a sequential retro-Michael addition/pyridine extrusion pathway.

Topics & Concepts

ChemistryCycloadditionPyridiniumConjugatePyridineAtom (system on chip)ExtrusionMichael reactionCombinatorial chemistryStereochemistryMedicinal chemistryCatalysisOrganic chemistryComputer scienceMathematicsMaterials scienceMetallurgyMathematical analysisEmbedded systemSynthesis and Catalytic ReactionsCatalytic C–H Functionalization MethodsOrganic Chemistry Cycloaddition Reactions
A New Reaction Mode of 3-Halooxindoles: Acting as C–C–O Three-Atom Components for (3+3) Cycloaddition to Access Indolenine-Fused 2<i>H</i>-1,4-Oxathiines | Litcius