State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
Nat Commun. 2020 Oct 23;11(1):5384. doi: 10.1038/s41467-020-19172-3.
Synergistic photoredox and copper catalysis confers new synthetic possibilities in the pharmaceutical field, but is seriously affected by the consumptive fluorescence quenching of Cu(II). By decorating bulky auxiliaries into a photoreductive triphenylamine-based ligand to twist the conjugation between the triphenylamine-based ligand and the polar Cu(II)-carboxylate node in the coordination polymer, we report a heterogeneous approach to directly confront this inherent problem. The twisted and polar Cu(II)-dye conjunction endows the coordination polymer with diode-like photoelectronic behaviours, which hampers the inter- and intramolecular photoinduced electron transfer from the triphenylamine-moiety to the Cu(II) site and permits reversed-directional ground-state electronic conductivity, rectifying the productive loop circuit for synergising photoredox and copper catalysis in pharmaceutically valuable decarboxylative C(sp)-heteroatom couplings. The well-retained Cu(II) sites during photoirradiation exhibit unique inner-spheric modulation effects, which endow the couplings with adaptability to different types of nucleophiles and radical precursors under concise reaction conditions, and distinguish the multi-olefinic moieties of biointeresting steride derivatives in their late-stage trifluoromethylation-chloration difunctionalisation.
协同光氧化还原和铜催化在制药领域赋予了新的合成可能性，但严重受到 Cu(II) 的消耗性荧光猝灭的影响。通过将大体积辅助剂修饰到基于三苯胺的光还原配体中，扭曲基于三苯胺的配体与配位聚合物中带电荷的 Cu(II)-羧酸盐节点之间的共轭，我们报告了一种直接解决这个固有问题的非均相方法。扭曲和带电荷的 Cu(II)-染料结合赋予了配位聚合物类似二极管的光电行为，这阻碍了从三苯胺部分到 Cu(II)位点的分子间和分子内光致电子转移，并允许反向的基态电子导电性，从而修正协同光氧化还原和铜催化在药物上有价值的脱羧 C(sp)-杂原子偶联中的生产回路。在光照射期间保留的 Cu(II)位点表现出独特的内球调制效应，这使得在简洁的反应条件下，偶联能够适应不同类型的亲核试剂和自由基前体，并在后期三氟甲基化-氯化双官能化过程中区分生物相关甾体衍生物的多烯烃部分。
