The cleavage and functionalization of C–S bonds have become a rapidly growing field for the design or discovery of new transformations. However, it is usually difficult to achieve in a direct and selective fashion due to the intrinsic inertness and catalyst-poisonous character. Herein, for the first time, we report a novel and efficient protocol that enables direct oxidative cleavage and cyanation of organosulfur compounds by heterogeneous nonprecious-metal Co-N-C catalyst comprising graphene encapsulated Co nanoparticles and Co-Nx sites using oxygen as environmentally benign oxidant and ammonia as nitrogen source. A wide variety of thiols, sulfides, sulfoxides, sulfones, sulfonamides, and sulfonyl chlorides are viable in this reaction, enabling access to diverse nitriles under cyanide-free conditions. Moreover, modifying the reaction conditions also allows for the cleavage and amidation of organosulfur compounds to deliver amides. This protocol features excellent functional group tolerance, facile scalability, cost-effective and recyclable catalyst, and broad substrate scope. Characterization and mechanistic studies reveal that the remarkable effectiveness of the synergistic catalysis of Co nanoparticles and Co-Nx sites is crucial for achieving outstanding catalytic performance.

C-S 键的裂解和功能化已成为设计或发现新转变的快速发展领域。然而，由于固有的惰性和催化剂有毒特性，通常很难以直接和选择性的方式实现。在此，我们首次报告了一种新颖有效的方案，该方案能够通过非贵金属 Co-NC 催化剂直接氧化裂解和氰化有机硫化合物，该催化剂包含石墨烯封装的 Co 纳米颗粒和 Co-Nx 位点，使用氧气作为环境友好的氧化剂和氨作为氮源。多种硫醇、硫化物、亚砜、砜、磺酰胺和磺酰氯在该反应中都是可行的，从而能够在无氰化物条件下获得多种腈。而且，改变反应条件还允许有机硫化合物的裂解和酰胺化以提供酰胺。该协议具有出色的官能团耐受性、易于扩展、具有成本效益和可回收的催化剂以及广泛的底物范围。表征和机理研究表明，Co 纳米粒子和 Co-Nx 位点协同催化的显着有效性对于实现出色的催化性能至关重要。