导读 近日,2021年化学诺奖得主、美国普林斯顿大学的David W. C. MacMillan教授课题组首次报道了一种基于双分子均裂取代(SH2)策略的光/镍协同催化自由基型交叉脱羧偶联反应,可用于由脂肪族羧酸出发构建有价值的C(sp3)-C(sp3)偶联产物。详细的机理实验表明该反应涉及Ni(III)-烷基物种与烷基自由基间的SH2过程。此外...
毫无疑问,该方法不仅进一步完善了C(sp3)-C(sp3)键偶联策略,而且为复杂分子的设计和合成提供了新策略。 A biomimeticSH2cross-coupling mechanism for quaternary sp3-carbon formation Wei Liu, Marissa N. Lavagnino, Colin A. Gould, Jesús Alcázar, David W. C. MacMillan Science,2021, DOI: 10.1126/scienc...
Artem V. Tsymbal, Lorenzo Delarue Bizzini, David W. C. MacMillan*. Nickel Catalysis via SH2 Homolytic Substitution: The Double Decarboxylative Cross-Coupling of Aliphatic Acids.J. Am. Chem. Soc., 2022. https://pubs.acs.org/doi/10.102...
这种异选自由基-自由基偶联利用铁卟啉的能力,很容易区分开壳伯碳和叔碳的SH2键形成作用,再结合光催化作用从广泛丰富的官能团中同时生成两类自由基。机理研究证实了偶联前一级烷基- fe (III)种的中间性,并为关键的四元sp3-碳键形成步骤中的SH2置换途径提供了证据。该工作以“A biomimeticSH2cross-coupling mechan...
Ruizhe Chen, Nicholas E. Intermaggio, Jiaxin Xie, James A. Rossi-Ashton, Colin A. Gould, Robert T. Martin, Jesús Alcázar, David W. C. MacMillan*. Alcohol-alcohol cross-coupling enabled by SH2 radical sorting. Science, 2024, science.org/doi/10.1126 发布于 2024-03-26 15:37・广东 ...
In this work, we report a nickel radical sorting–mediated cross-alcohol coupling wherein two alcohol fragments are deoxygenated and coupled in one reaction vessel, open to air.Ruizhe ChenNicholas E. IntermaggioJiaxin XieJames A. Rossi-Ashton...
Ruizhe Chen, Nicholas E. Intermaggio, Jiaxin Xie, James A. Rossi-Ashton, Colin A. Gould, Robert T. Martin, Jesús Alcázar, David W. C. MacMillan*. Alcohol-alcohol cross-coupling enabled by SH2 radical sorting.Science,2024, https://www.science.org/doi/10.1126/science.adl5890...
The required F2pmp building block was directly synthesized by copper mediated cross coupling of an organozinc compound in analogy to published procedures [26–31]. SH2 enrichment The probe was immobilized on sepharose beads and pull-down experiments were performed using mixed cell lysates (Colo205,...
c Cross-over experiment between 80 and 81. d The three-component cross-coupling. e Plausible mechanism. Full size image Interestingly, when Fe(TPP)(III)Cl was used as the catalyst, no decarboxylative C-N coupling occurred (Fig. 5b). However, when 50 mol% amount of NaI was added to ...
Artem V. Tsymbal, Lorenzo Delarue Bizzini, David W. C. MacMillan*. Nickel Catalysis via SH2 Homolytic Substitution: The Double Decarboxylative Cross-Coupling of Aliphatic Acids. J. Am. Chem. Soc., 2022. https://pubs.acs.org/doi/10.1021/jacs.2c08989...