Li Quanzhe, Gu Xintao, Wei Yin, Shi Min
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology 130 Meilong Road Shanghai 200237 China
Chem Sci. 2022 Sep 16;13(39):11623-11632. doi: 10.1039/d2sc02822k. eCollection 2022 Oct 12.
Despite significant advances made on the synthesis of indole derivatives through photochemical strategies during the past several years, the requirement of equivalent amounts of oxidants, bases or other additional additives has limited their practical applications in the synthesis of natural products and pharmaceuticals as environment-friendly processes. Herein, we report LED visible-light-induced redox neutral desulfonylative C(sp)-H functionalization for the synthesis of -substituted indoles with a broad scope through γ-fragmentation under mild conditions in the absence of any additional additive. The reaction mechanism paradigm has been investigated on the basis of deuterium labeling experiments, kinetic analysis, Hammett plotting analysis and DFT calculations.
尽管在过去几年中通过光化学策略合成吲哚衍生物取得了显著进展，但需要等量的氧化剂、碱或其他额外添加剂，这限制了它们作为环境友好型工艺在天然产物和药物合成中的实际应用。在此，我们报道了LED可见光诱导的氧化还原中性脱磺酰基C(sp)-H官能化反应，该反应在温和条件下，无需任何额外添加剂，通过γ-碎片化反应，可广泛用于合成各种β-取代吲哚。我们基于氘代标记实验、动力学分析、哈米特绘图分析和密度泛函理论计算，对反应机理进行了研究。
