Shangwen Fang, Yu Liu, Fei Wang, Yue Zhao, Congqing Zhu, Yuncong Chen, Sergey N. Konchenko, Jing Zhao, Jie Han, Jin Xie
{"title":"协同双核金催化解锁氧化C-C偶联中的1,2-还原消除元素反应","authors":"Shangwen Fang, Yu Liu, Fei Wang, Yue Zhao, Congqing Zhu, Yuncong Chen, Sergey N. Konchenko, Jing Zhao, Jie Han, Jin Xie","doi":"10.1002/anie.202506925","DOIUrl":null,"url":null,"abstract":"<p>Cooperative catalysis enabled by dinuclear metal complexes can integrate the catalytic properties of each metal center, thus opening new avenues to achieve challenging reaction selectivity that are difficult to accomplish with mononuclear metal catalysts. Here, we present a cooperative catalysis strategy using a newly synthesized dinuclear PNP-Au<sub>2</sub> catalyst, which positions two gold centers in close proximity, facilitating favorable geometric and electronic interactions for the synergistic activation of both coupling partners (alkynes and vinyl boron reagents) in the oxidative C─C coupling. It demonstrates a broad substrate tolerance for both terminal and internal alkynes, providing a versatile platform for the synthesis of enynes and dienes. Mechanistic and computational studies reveal a unique 1,2-cooperative activation mode, significantly reducing the free energy barrier and stabilizing the key intermediates, thus promoting C─C bond formation in an efficient manner. The DFT calculations indicate a less explored 1,2-reductive elimination elementary step. Interestingly, the use of B(O<i><sup>i</sup></i>Pr)<sub>3</sub> as an additive can effectively prevent the decomposition of dinuclear gold catalyst under oxidative fluoride-containing conditions.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"64 26","pages":""},"PeriodicalIF":16.1000,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Cooperative Dinuclear Gold Catalysis Unlocking 1,2-Reductive Elimination Elementary Reaction in Oxidative C─C Coupling\",\"authors\":\"Shangwen Fang, Yu Liu, Fei Wang, Yue Zhao, Congqing Zhu, Yuncong Chen, Sergey N. Konchenko, Jing Zhao, Jie Han, Jin Xie\",\"doi\":\"10.1002/anie.202506925\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Cooperative catalysis enabled by dinuclear metal complexes can integrate the catalytic properties of each metal center, thus opening new avenues to achieve challenging reaction selectivity that are difficult to accomplish with mononuclear metal catalysts. Here, we present a cooperative catalysis strategy using a newly synthesized dinuclear PNP-Au<sub>2</sub> catalyst, which positions two gold centers in close proximity, facilitating favorable geometric and electronic interactions for the synergistic activation of both coupling partners (alkynes and vinyl boron reagents) in the oxidative C─C coupling. It demonstrates a broad substrate tolerance for both terminal and internal alkynes, providing a versatile platform for the synthesis of enynes and dienes. Mechanistic and computational studies reveal a unique 1,2-cooperative activation mode, significantly reducing the free energy barrier and stabilizing the key intermediates, thus promoting C─C bond formation in an efficient manner. The DFT calculations indicate a less explored 1,2-reductive elimination elementary step. Interestingly, the use of B(O<i><sup>i</sup></i>Pr)<sub>3</sub> as an additive can effectively prevent the decomposition of dinuclear gold catalyst under oxidative fluoride-containing conditions.</p>\",\"PeriodicalId\":125,\"journal\":{\"name\":\"Angewandte Chemie International Edition\",\"volume\":\"64 26\",\"pages\":\"\"},\"PeriodicalIF\":16.1000,\"publicationDate\":\"2025-04-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Angewandte Chemie International Edition\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/anie.202506925\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/anie.202506925","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Cooperative catalysis enabled by dinuclear metal complexes can integrate the catalytic properties of each metal center, thus opening new avenues to achieve challenging reaction selectivity that are difficult to accomplish with mononuclear metal catalysts. Here, we present a cooperative catalysis strategy using a newly synthesized dinuclear PNP-Au2 catalyst, which positions two gold centers in close proximity, facilitating favorable geometric and electronic interactions for the synergistic activation of both coupling partners (alkynes and vinyl boron reagents) in the oxidative C─C coupling. It demonstrates a broad substrate tolerance for both terminal and internal alkynes, providing a versatile platform for the synthesis of enynes and dienes. Mechanistic and computational studies reveal a unique 1,2-cooperative activation mode, significantly reducing the free energy barrier and stabilizing the key intermediates, thus promoting C─C bond formation in an efficient manner. The DFT calculations indicate a less explored 1,2-reductive elimination elementary step. Interestingly, the use of B(OiPr)3 as an additive can effectively prevent the decomposition of dinuclear gold catalyst under oxidative fluoride-containing conditions.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.