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The synthetic potential of thiophenols as a protic nucleophilic trigger in the transition-metal-free and Grignard-reagent-free three-component coupling involving arynes is demonstrated. Employing aldehydes as the third component, the reaction allowed the mild and broad scope synthesis of 2-arylthio benzyl alcohol derivatives in good yields. Moreover, selenophenol could be used as the nucleophilic trigger, and activated ketones could be used as the third component in this reaction.Controllable rhodium(III)-catalyzed tandem [3+2] cyclizati
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