Abstract

A synergistic dual catalysis approach involving gold and copper catalysts for the synthesis of macrolactones bearing 1,3‐butadiynes through an intramolecular Glaser–Hay coupling reaction in good yield is described. This dual catalytic system exhibited good selectivity, reactivity and functional group tolerance. This unique process offers a paradigm shift: the potential as well as the versatility of this novel method is not only exemplified for the synthesis of macrolactones of different ring size but also for the rapid total synthesis of ivorenolide B, a new class of macrolides endowed with conjugated 1,3‐diyne motif, having impressive immunosuppressive activities.

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