镍催化还原偶联策略高效制备不对称二硫醚。
Efficient preparation of unsymmetrical disulfides by nickel-catalyzed reductive coupling strategy.
机构信息
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Suzhou Nano Science and Technology Soochow University, Suzhou, 215123, China.
Key Laboratory of Biomass-based Green Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Nanjing, 210037, China.
出版信息
Nat Commun. 2022 May 11;13(1):2588. doi: 10.1038/s41467-022-30256-0.
Disulfides are widely found in natural products and find a wide range of applications in life sciences, materials chemistry and other fields. The preparation of disulfides mainly rely on oxidative couplings of two sulfur containing compounds. This strategy has many side reactions and other shortcomings. Herein, we describe the reductive nickel-catalyzed cross-electrophile coupling of unactivated alkyl bromides with symmetrical alkyl- and aryltetrasulfides to form alkyl-alkyl and aryl-alkyl unsymmetrical disulfides. This approach for disulfide synthesis is practical, relies on easily available, unfunctionalized substrates, and is scalable. We investigated the mechanism of this transformation and found that the tetrasulfide compound does not selectively break the central S-S bond, but regio-selectively generates trisulfide intermediates.
二硫键广泛存在于天然产物中，在生命科学、材料化学等领域有着广泛的应用。二硫键的制备主要依赖于两个含硫化合物的氧化偶联。该策略存在许多副反应和其他缺点。在此，我们描述了镍催化的还原交叉亲电试剂偶联反应，可实现未活化的烷基溴化物与对称的烷基和芳基四硫化物之间形成烷基-烷基和芳基-烷基不对称二硫键。这种合成二硫键的方法具有实用性，它依赖于易得的、无功能化的底物，并且可以进行规模化。我们研究了这种转化的反应机理，发现四硫化物化合物不会选择性地断裂中心 S-S 键，而是区域选择性地生成三硫化物中间体。
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