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Multicomponent ring-opening/Huisgen cycloaddition reactions combined with CO2 capture with a polyurea-encapsulated copper salt as a catalyst that in situ formed from simple CuCl and soluble polyurea during the reaction were carried out successfully for the synthesis of β-hydroxytriazoles under exceptionally mild conditions, in which the polyurea-encapsulated copper(i) chloride proved to be a robust and recyclable catalyst system with high yields as well as excellent chemoselectivity in this reaction. [ABSTRACT FROM AUTHOR]