Lixue Zhang , Guoyu Cheng , Fabin Zhou , Xin Yang , Huicheng Cheng , Mei Yu , Dahong Jiang , Peng Zhou , He Yang , Bingxin Yuan , Wenjun Tang , Ji-cheng Shi
{"title":"terphenyl phospine TRuPhos:钯催化受阻伯烷基胺芳基化的新型高效配体及其机理澄清","authors":"Lixue Zhang , Guoyu Cheng , Fabin Zhou , Xin Yang , Huicheng Cheng , Mei Yu , Dahong Jiang , Peng Zhou , He Yang , Bingxin Yuan , Wenjun Tang , Ji-cheng Shi","doi":"10.1016/j.jcat.2025.116391","DOIUrl":null,"url":null,"abstract":"<div><div>Terphenyl phosphines are rising as powerful supporting ligands in the palladium-catalyzed C-N cross-coupling reactions, leading to reduced catalyst loadings and broadened substrate scope. To extend the terphenyl phosphine family, TRuPhos and TSPhos along with their 2-amino-biphenyl-ƞ<sup>2</sup>-C,N palladium precatalysts have been synthesized and characterized, including one complex by single-crystal diffraction. TRuPhos exhibits unprecedented efficiency in the palladium-catalyzed arylation of many hindered primary alkyl amines. Mechanism studies have clarified that: 1) the transmetalation <strong>path A</strong> involving amine adducts of oxidative addition product does not work by the TRuPhos-supported palladium catalyst in the arylation of hindered primary alkyl amines, but works for that in small bulk amines; 2) the <strong>path C</strong> involving the substitution of halogen atoms on oxidative addition products by <em>t</em>BuO groups seems impossible as well; 3) the reaction occurred between oxidative addition products and sodium amides forming C-N coupling products suggests that <strong>path B</strong> is a possible transmetalation pathway in Pd/TRuPhos-catalyzed arylation of hindered primary alkyl amines.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116391"},"PeriodicalIF":6.5000,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"The terphenyl phosphine TRuPhos: a novel and efficient ligand for the palladium-catalyzed arylation of hindered primary alkyl amines with mechanism clarification\",\"authors\":\"Lixue Zhang , Guoyu Cheng , Fabin Zhou , Xin Yang , Huicheng Cheng , Mei Yu , Dahong Jiang , Peng Zhou , He Yang , Bingxin Yuan , Wenjun Tang , Ji-cheng Shi\",\"doi\":\"10.1016/j.jcat.2025.116391\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Terphenyl phosphines are rising as powerful supporting ligands in the palladium-catalyzed C-N cross-coupling reactions, leading to reduced catalyst loadings and broadened substrate scope. To extend the terphenyl phosphine family, TRuPhos and TSPhos along with their 2-amino-biphenyl-ƞ<sup>2</sup>-C,N palladium precatalysts have been synthesized and characterized, including one complex by single-crystal diffraction. TRuPhos exhibits unprecedented efficiency in the palladium-catalyzed arylation of many hindered primary alkyl amines. Mechanism studies have clarified that: 1) the transmetalation <strong>path A</strong> involving amine adducts of oxidative addition product does not work by the TRuPhos-supported palladium catalyst in the arylation of hindered primary alkyl amines, but works for that in small bulk amines; 2) the <strong>path C</strong> involving the substitution of halogen atoms on oxidative addition products by <em>t</em>BuO groups seems impossible as well; 3) the reaction occurred between oxidative addition products and sodium amides forming C-N coupling products suggests that <strong>path B</strong> is a possible transmetalation pathway in Pd/TRuPhos-catalyzed arylation of hindered primary alkyl amines.</div></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":\"451 \",\"pages\":\"Article 116391\"},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2025-08-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951725004579\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951725004579","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
The terphenyl phosphine TRuPhos: a novel and efficient ligand for the palladium-catalyzed arylation of hindered primary alkyl amines with mechanism clarification
Terphenyl phosphines are rising as powerful supporting ligands in the palladium-catalyzed C-N cross-coupling reactions, leading to reduced catalyst loadings and broadened substrate scope. To extend the terphenyl phosphine family, TRuPhos and TSPhos along with their 2-amino-biphenyl-ƞ2-C,N palladium precatalysts have been synthesized and characterized, including one complex by single-crystal diffraction. TRuPhos exhibits unprecedented efficiency in the palladium-catalyzed arylation of many hindered primary alkyl amines. Mechanism studies have clarified that: 1) the transmetalation path A involving amine adducts of oxidative addition product does not work by the TRuPhos-supported palladium catalyst in the arylation of hindered primary alkyl amines, but works for that in small bulk amines; 2) the path C involving the substitution of halogen atoms on oxidative addition products by tBuO groups seems impossible as well; 3) the reaction occurred between oxidative addition products and sodium amides forming C-N coupling products suggests that path B is a possible transmetalation pathway in Pd/TRuPhos-catalyzed arylation of hindered primary alkyl amines.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.