Oxidative cleavage and ammoxidation of organosulfur compounds via synergistic Co-Nx sites and Co nanoparticles catalysis
Abstract 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...
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2023-05-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-38614-2 |
| _version_ | 1797817906184060928 |
|---|---|
| author | Huihui Luo Shuainan Tian Hongliang Liang He Wang Shuang Gao Wen Dai |
| author_facet | Huihui Luo Shuainan Tian Hongliang Liang He Wang Shuang Gao Wen Dai |
| author_sort | Huihui Luo |
| collection | DOAJ |
| description | Abstract 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. |
| first_indexed | 2024-03-13T09:00:23Z |
| format | Article |
| id | doaj.art-5198965bdce741bcbffb11eed1ec7272 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-13T09:00:23Z |
| publishDate | 2023-05-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-5198965bdce741bcbffb11eed1ec72722023-05-28T11:21:00ZengNature PortfolioNature Communications2041-17232023-05-0114111310.1038/s41467-023-38614-2Oxidative cleavage and ammoxidation of organosulfur compounds via synergistic Co-Nx sites and Co nanoparticles catalysisHuihui Luo0Shuainan Tian1Hongliang Liang2He Wang3Shuang Gao4Wen Dai5Dalian Institute of Chemical Physics, Chinese Academy of SciencesDalian Institute of Chemical Physics, Chinese Academy of SciencesDalian Institute of Chemical Physics, Chinese Academy of SciencesSchool of Chemistry and Materials Science, Liaoning Shihua UniversityDalian Institute of Chemical Physics, Chinese Academy of SciencesDalian Institute of Chemical Physics, Chinese Academy of SciencesAbstract 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.https://doi.org/10.1038/s41467-023-38614-2 |
| spellingShingle | Huihui Luo Shuainan Tian Hongliang Liang He Wang Shuang Gao Wen Dai Oxidative cleavage and ammoxidation of organosulfur compounds via synergistic Co-Nx sites and Co nanoparticles catalysis Nature Communications |
| title | Oxidative cleavage and ammoxidation of organosulfur compounds via synergistic Co-Nx sites and Co nanoparticles catalysis |
| title_full | Oxidative cleavage and ammoxidation of organosulfur compounds via synergistic Co-Nx sites and Co nanoparticles catalysis |
| title_fullStr | Oxidative cleavage and ammoxidation of organosulfur compounds via synergistic Co-Nx sites and Co nanoparticles catalysis |
| title_full_unstemmed | Oxidative cleavage and ammoxidation of organosulfur compounds via synergistic Co-Nx sites and Co nanoparticles catalysis |
| title_short | Oxidative cleavage and ammoxidation of organosulfur compounds via synergistic Co-Nx sites and Co nanoparticles catalysis |
| title_sort | oxidative cleavage and ammoxidation of organosulfur compounds via synergistic co nx sites and co nanoparticles catalysis |
| url | https://doi.org/10.1038/s41467-023-38614-2 |
| work_keys_str_mv | AT huihuiluo oxidativecleavageandammoxidationoforganosulfurcompoundsviasynergisticconxsitesandconanoparticlescatalysis AT shuainantian oxidativecleavageandammoxidationoforganosulfurcompoundsviasynergisticconxsitesandconanoparticlescatalysis AT hongliangliang oxidativecleavageandammoxidationoforganosulfurcompoundsviasynergisticconxsitesandconanoparticlescatalysis AT hewang oxidativecleavageandammoxidationoforganosulfurcompoundsviasynergisticconxsitesandconanoparticlescatalysis AT shuanggao oxidativecleavageandammoxidationoforganosulfurcompoundsviasynergisticconxsitesandconanoparticlescatalysis AT wendai oxidativecleavageandammoxidationoforganosulfurcompoundsviasynergisticconxsitesandconanoparticlescatalysis |