近日，杭州师范大学邵欣欣团队报道了硫醇锌的发现：镍催化还原性C(sp²)-S偶联中缺失的环节。2026年3月10日出版的《中国化学》杂志发表了这一最新研究成果。

镍催化有机卤化物与硫亲电试剂的还原偶联反应已成为构建多样化含硫分子的重要策略。然而，由于对多种镍中间体（如Ni(I)/Ni(II)/Ni(III)）的表征研究不足，以及金属还原添加剂在机理中的作用尚未明确，该反应的机理仍未完全阐明。

研究组发现，锌对二硫化物中S–S键的快速氧化加成是实现与芳基镍(II)加合物后续金属交换的关键步骤。此外，研究组揭示了锌的另一双重关键作用：既可将Ni(II)预催化剂还原为活性Ni(0)物种，又能介导硫亲电试剂（如N-硫代邻苯二甲酰亚胺或硫代磺酸酯）还原为相应的二硫化物。研究组还首次报道了无碱条件下镍催化的Negishi型硫醇化反应，该反应使用可常温稳定保存的二硫醇锌盐与（杂）芳基卤化物偶联，为合成结构多样的富含C(sp²)硫化物提供了超越现有方法学的通用替代方案。

附：英文原文

Title: Discovery of Zinc Thiolates as the Missing Link in Ni-Catalyzed Reductive C(sp)2–S Coupling†

Author: Han Qian, Yuenian Xu, Wenlei Zhang, Zihan Liu, Ying Bai, Xinxin Shao

Issue&Volume: 2026-03-10

Abstract: Nickel-catalyzed reductive coupling of organic halides with sulfur electrophiles has emerged as a robust strategy for accessing a diverse array of valuable sulfur-containing molecules. However, its mechanism remains incompletely elucidated, primarily due to the lack of studies on characterization of multiple nickel intermediates (e.g., Ni(I)/Ni(II)/Ni(III)), as well as the mechanistic roles of reductive metal additives. Herein, we identify the rapid oxidative addition of zinc to the S–S bond of disulfides as a pivotal step that enables subsequent transmetallation with arylnickel(II) adducts. Furthermore, we discovered that the zinc serves as additional two critical roles: it not only reduces the Ni(II)-precatalyst to active Ni(0) specie, but also mediates the reduction of sulfur electrophiles (e.g., N-thiophthalimides or thiosulfonates) to the corresponding disulfides. We also report the first example of a base-free, nickel-catalyzed Negishi-type thiolation of (hetero)aryl halides using bench-stable zinc dithiolates, thereby furnishing a versatile alternative to established methodologies for the synthesis of structurally diverse C(sp2)-rich sulfides.

DOI: 10.1002/cjoc.70533

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70533