The Different Faces of [Ru(bpy)3Cl2] and fac[Ir(ppy)3] Photocatalysts: Redox Potential Controlled Synthesis of Sulfonylated Fluorenes and Pyrroloindoles from Unactivated Olefins and Sulfonyl Chlorides.
The Different Faces of [Ru(bpy)3Cl2] and fac[Ir(ppy)3] Photocatalysts: Redox Potential Controlled Synthesis of Sulfonylated Fluorenes and Pyrroloindoles from Unactivated Olefins and Sulfonyl Chlorides.
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DOI：
10.1021/acs.orglett.0c02760
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发表时间：
2020-09
期刊：
影响因子：
5.2
通讯作者：
Santosh K Pagire;N. Kumagai;M. Shibasaki
中科院分区：
文献类型：
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作者：
Santosh K Pagire;N. Kumagai;M. Shibasaki
同时生成C-S键和C-C键的级联烯烃磺化反应是一种高效、有效的方法，可在一次操作中直接获得结构多样的磺化化合物。该反应是以FeC[Ir(Ppy)3]为光催化剂，通过磺酰氯与2-芳基苯乙烯的区域选择性自由基加成反应实现的，显示了其在原子转移自由基加成(ATRA)继而光环化的光级联过程中的独特作用。通过这种光级联反应，以极高的产率合成了一类在光电材料和药物化学领域有应用价值的新的磺酰基取代荧烯和吡咯吲哚。相反，当使用还原电位较低的[Ru(Bpy)3Cl2]催化剂时，环化反应被中断，只导致C-S键的形成和在相同反应条件下生成无环的磺酰化2-芳基苯乙烯。本发明的室温光催化的综合用途由于广泛可获得台架稳定的磺酰氯和未活化的烯烃而得到加强，从而提供了一种经济有效和范围广泛的方案。
A cascade alkene sulfonylation that simultaneously forges C-S and C-C bonds is a highly efficient and powerful approach for directly accessing structurally diverse sulfonylated compounds in a single operation. The reaction was enabled by visible-light-mediated regioselective radical addition of sulfonyl chlorides to 2-arylstyrenes using fac[Ir(ppy)3] as a photocatalyst, demonstrating its unique role in a photocascade process to execute atom transfer radical addition (ATRA) followed by photocyclization. A new class of sulfonyl-substituted fluorenes and pyrroloindoles, which are useful in the field of photoelectronic materials and medicinal chemistry, was produced in excellent yields by this photocascade reaction. In contrast, the cyclization was interrupted when using the [Ru(bpy)3Cl2] catalyst having lower reduction potential, leading only to the formation of a C-S bond and the production of acyclic sulfonylated 2-arylstyrenes under identical reaction conditions. The synthetic utility of the present room-temperature photocatalysis is enhanced by the broad availability of bench-stable sulfonyl chlorides and unactivated olefins, thereby providing a cost-effective and broad-scope protocol.