Kinetics of Palladium(0)‐Allyl Interactions in the Tsuji‐Trost Reaction, derived from Single‐Molecule Fluorescence Microscopy,ChemCatChem

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Kinetics of Palladium(0)‐Allyl Interactions in the Tsuji‐Trost Reaction, derived from Single‐Molecule Fluorescence Microscopy
ChemCatChem ( IF 3.8 ) Pub Date : 2020-04-01 , DOI: 10.1002/cctc.202000032
Johannes A. Menges ₁ , Alexander Grandjean ₁ , Anne Clasen ₁ , Gregor Jung ₁

Affiliation

Single‐molecule (SM) chemistry is devoted to unravel reaction steps which are hidden in cuvette experiments. Controversies about the substrate activation during the Tsuji‐Trost deallylation motivated us to study, on the single‐molecule level, the kinetics of the catalyst precursor Pd(PPh₃)₄ with our recently designed two‐color fluorescent probes. Photochemical, metal‐free bypass reactions were found and taken into account by the combination of spectrally separated single‐molecule TIRF‐microscopy and state‐of‐the art analysis procedures. Unselective π‐complex formation (K_D≈10³ M⁻¹) precedes the insertion of the active catalyst into the C−OR bond (RO⁻=leaving group), indicated by the lacking immediate change of fluorescence color. The formed intermediate then decomposes on a time scale of≥2 – 3 s to the deallylated product.

中文翻译：

Tsuji-Trost反应中钯（0）-烯丙基相互作用的动力学，源自单分子荧光显微镜

单分子（SM）化学致力于解开反应杯实验中隐藏的反应步骤。关于Tsuji-Trost脱羧反应中底物活化的争论促使我们用我们最近设计的双色荧光探针在单分子水平上研究催化剂前驱体Pd（PPh ₃）₄的动力学。通过光谱分离的单分子TIRF显微镜和最新的分析程序相结合，发现并考虑了光化学，无金属的旁路反应。非选择性的π共复合物形成（K _d ≈10 ³ 中号^-1）之前的活性催化剂到C-OR键（RO的插入^-=离开组），由荧光颜色的立即变化所指示。所形成的中间体然后在≥2-3秒的时间范围内分解为脱羧产物。

更新日期：2020-04-01

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