A stereoselective synthesis of the spirolactam fragment (C31–C41) of a highly‐potent immunosuppressant sanglifehrin A is described. The key steps involved in this synthesis are a desymmetrization protocol, Sharpless asymmetric epoxidation, Crimmins syn aldol reaction, Barton–McCombie deoxygenation, and acid‐mediated spirolactamization.

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.

No abstract

The Front Cover shows an example of synergistic catalysis, an advanced synthetic strategy that involves the concurrent activation of both nucleophile and electrophile simultaneously by two separate and distinct catalysts to afford a single chemical transformation. In this case, gold and copper are used as synergistic catalysts for the synthesis of macrolactones bearing 1,3‐butadiynes through an intramolecular Glaser–Hay coupling reaction in good yield. The potential, as well as the versatility, of this novel method is not only exemplified by the synthesis of macrolactones of different ring size, but also by the rapid total synthesis of ivorenolide B, a new class of macrolide endowed with a conjugated 1,3‐diyne motif that has impressive immunosuppressive activities. More information can be found in the https://doi.org/10.1002/ejoc.201800708