Design, synthesis and visible-light-induced non-radical reactions of dual-functional Rh catalysts
Design, synthesis and visible-light-induced non-radical reactions of dual-functional Rh catalysts
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DOI：
10.1038/s44160-023-00268-9
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发表时间：
2023-03
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影响因子：
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通讯作者：
Seiya Ouchi;Tomonori Inoue;Juntaro Nogami;Yuki Nagashima;Ken Tanaka
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文献类型：
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作者：
Seiya Ouchi;Tomonori Inoue;Juntaro Nogami;Yuki Nagashima;Ken Tanaka
与包含过渡金属和光氧化还原催化剂的二元催化系统相比，在单催化循环中操作的过渡金属光诱导催化剂是优选的。这种单催化剂体系具有可见光吸收和化学转化的双重功能。然而，大多数可见光驱动的催化反应是通过自由基机制进行的，这限制了催化剂适用的反应类型。一些非自由基催化反应已经被开发出来，但由于催化剂的低可见光捕获能力，这些反应依赖于底物。本文报道了双功能Rh催化剂螺芴-独立烯基(SFI)-Rh(I)配合物的设计、合成和可见光诱导的非自由基反应。具有非融合但π扩展配体的SFI-Rh(I)配合物由于具有较高的可见光捕获能力而降低了对底物的依赖性，并且由于抗质子化而表现出较高的稳定性。因此，SFI-Rh(I)催化剂将典型的Rh(I)催化反应（如芳烃的C-H硼化反应和炔的[2+2+2]环加成反应）的范围扩展到室温下蓝色发光二极管照射下具有挑战性的底物。
Transition metal photo-induced catalysts operating in a single catalytic cycle are preferable compared with binary catalytic systems comprising both transition metal and photoredox catalysts. Such single-catalyst systems perform the dual function of visible light absorption and chemical transformation. However, most visible-light-driven catalytic reactions proceed via radical mechanisms, limiting the reaction types to which the catalysts are applicable. Several non-radical catalytic reactions have been developed, but these reactions are substrate dependent owing to the low visible-light-harvesting ability of the catalysts. Here we report the design, synthesis and visible-light-induced non-radical reactions of dual-functional Rh catalysts, spiro-fluorene-indenoindenyl (SFI)-Rh(I) complexes. The SFI-Rh(I) complexes with non-fused but π-extended ligands reduce substrate dependence owing to high visible-light-harvesting ability, and show high stability due to resistance against protonation. Thus, the SFI-Rh(I) catalysts extend the scope of typical Rh(I)-catalysed reactions, such as the C–H borylation of arenes and [2+2+2] cycloaddition of alkynes, to challenging substrates under blue light-emitting diode irradiation at room temperature.