Macrocycles have fascinated scientists for over half a century due to their aesthetically appealing structures and broad utilities in chemical, material, and biological research. However, the efficient preparation of macrocycles remains an ongoing research challenge in organic synthesis because of the high entropic penalty involved in the ring-closing process. Herein we report a photocatalyzed thiol-yne click reaction to forge diverse sulfur-containing macrocycles (up to 35-membered ring) and linear C2-linked 1,2-(S-S/S-P/S-N) functionalized molecules, starting from the simplest alkyne, acetylene. Preliminary mechanistic experiments support a visible light-mediated radical-polar crossover dihydrothiolation process. This operationally straightforward reaction is also amenable to the synthesis of organometallic complexes, bis-sulfoxide ligand and a pleuromutilin antibiotic drug Tiamulin, which provides a practical route to synthesize highly valued compounds from the feedstock acetylene gas.

半个多世纪以来，大环化合物因其美观的结构和在化学、材料和生物学研究中的广泛用途而吸引了科学家们的注意。然而，由于闭环过程中涉及高熵损失，大环化合物的有效制备仍然是有机合成中持续的研究挑战。在这里，我们报道了一种光催化的硫醇-炔点击反应，从最简单的炔烃开始，形成多种含硫大环（最多 35 元环）和线性 C2 连接的 1,2-(SS/SP/SN) 功能化分子，乙炔。初步的机械实验支持可见光介导的自由基-极性交叉二氢硫醇化过程。这种操作简单的反应也适用于有机金属配合物的合成，