Dr. Diego R. Javier-Jiménez, Dr. Matthew B. Reuter, Emma J. Finfer, Gavin A. Sicard, Prof. Dr. Rory Waterman
{"title":"I族叔戊酯:氢膦化反应的比较研究","authors":"Dr. Diego R. Javier-Jiménez, Dr. Matthew B. Reuter, Emma J. Finfer, Gavin A. Sicard, Prof. Dr. Rory Waterman","doi":"10.1002/cctc.202500752","DOIUrl":null,"url":null,"abstract":"<p>The first comparative study of group I elements in hydrophosphination catalysis is presented, which identifies hydrophosphination catalyzed by rubidium and cesium compounds for the first time. Catalytic activity increases down the group with a step up in reactivity past the third period. Despite the differences in activity, the trends in reactivity are consistent with nucleophilicity, as evidenced by a Hammett analysis. Radical reactivity was eliminated through EPR monitoring under catalytic conditions. Information from deuterium labeling experiments was limited due to the basicity of the precatalysts and an apparent sigmatropic shift. Overall, enhanced hydrophosphination activity from group I metals is observed that is competitive with transition-metal catalysts for even modestly activated unsaturated substrates. Optimization through a few key factors may be exportable for further development, even if the substrate scope for group I elements is not yet as broad as it is for transition-metal catalysts.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9000,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500752","citationCount":"0","resultStr":"{\"title\":\"Group I tert-Amylates: A Comparative Study in Hydrophosphination Reactions\",\"authors\":\"Dr. Diego R. Javier-Jiménez, Dr. Matthew B. Reuter, Emma J. Finfer, Gavin A. Sicard, Prof. Dr. Rory Waterman\",\"doi\":\"10.1002/cctc.202500752\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The first comparative study of group I elements in hydrophosphination catalysis is presented, which identifies hydrophosphination catalyzed by rubidium and cesium compounds for the first time. Catalytic activity increases down the group with a step up in reactivity past the third period. Despite the differences in activity, the trends in reactivity are consistent with nucleophilicity, as evidenced by a Hammett analysis. Radical reactivity was eliminated through EPR monitoring under catalytic conditions. Information from deuterium labeling experiments was limited due to the basicity of the precatalysts and an apparent sigmatropic shift. Overall, enhanced hydrophosphination activity from group I metals is observed that is competitive with transition-metal catalysts for even modestly activated unsaturated substrates. Optimization through a few key factors may be exportable for further development, even if the substrate scope for group I elements is not yet as broad as it is for transition-metal catalysts.</p>\",\"PeriodicalId\":141,\"journal\":{\"name\":\"ChemCatChem\",\"volume\":\"17 18\",\"pages\":\"\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-07-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500752\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemCatChem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202500752\",\"RegionNum\":3,\"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":"ChemCatChem","FirstCategoryId":"92","ListUrlMain":"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202500752","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Group I tert-Amylates: A Comparative Study in Hydrophosphination Reactions
The first comparative study of group I elements in hydrophosphination catalysis is presented, which identifies hydrophosphination catalyzed by rubidium and cesium compounds for the first time. Catalytic activity increases down the group with a step up in reactivity past the third period. Despite the differences in activity, the trends in reactivity are consistent with nucleophilicity, as evidenced by a Hammett analysis. Radical reactivity was eliminated through EPR monitoring under catalytic conditions. Information from deuterium labeling experiments was limited due to the basicity of the precatalysts and an apparent sigmatropic shift. Overall, enhanced hydrophosphination activity from group I metals is observed that is competitive with transition-metal catalysts for even modestly activated unsaturated substrates. Optimization through a few key factors may be exportable for further development, even if the substrate scope for group I elements is not yet as broad as it is for transition-metal catalysts.
期刊介绍:
With an impact factor of 4.495 (2018), ChemCatChem is one of the premier journals in the field of catalysis. The journal provides primary research papers and critical secondary information on heterogeneous, homogeneous and bio- and nanocatalysis. The journal is well placed to strengthen cross-communication within between these communities. Its authors and readers come from academia, the chemical industry, and government laboratories across the world. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies, and is supported by the German Catalysis Society.