Group I tert-Amylates: A Comparative Study in Hydrophosphination Reactions

IF 3.9 3区 化学 Q2 CHEMISTRY, PHYSICAL
ChemCatChem Pub Date : 2025-07-15 DOI:10.1002/cctc.202500752
Dr. Diego R. Javier-Jiménez, Dr. Matthew B. Reuter, Emma J. Finfer, Gavin A. Sicard, Prof. Dr. Rory Waterman
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引用次数: 0

Abstract

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.

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I族叔戊酯:氢膦化反应的比较研究
首次对氢磷化催化中的I族元素进行了比较研究,首次确定了铷和铯化合物催化的氢磷化反应。催化活性随着第三期后反应活性的增加而降低。尽管活性不同,但反应性的趋势与亲核性一致,如Hammett分析所证明的那样。在催化条件下,通过EPR监测消除了自由基反应性。由于预催化剂的碱度和明显的符号变换,氘标记实验的信息有限。总的来说,观察到I族金属的氢磷化活性增强,即使是适度活化的不饱和底物,也与过渡金属催化剂竞争。通过几个关键因素进行优化可以为进一步的开发提供借鉴,即使I族元素的衬底范围还没有过渡金属催化剂那么广泛。
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来源期刊
ChemCatChem
ChemCatChem 化学-物理化学
CiteScore
8.10
自引率
4.40%
发文量
511
审稿时长
1.3 months
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.
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