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A highly efficient heterogeneous copper(I)‐catalyzed three‐component coupling of terminal alkynes, diazoesters and aldehydes has been achieved by using 10 mol% of copper(I) iodide complex [N,N‐CuI‐MCM‐41] anchored on 2‐aminoethylamino‐modified mesoporous material MCM‐41 as the catalyst under mild conditions, delivering a wide variety of 2‐alkoxycarbonyl‐substituted (E)‐1,3‐enynes in mostly good to...