Asymmetric vicinal C(sp 3 )–H difunctionalization of saturated cyclic amines via synergistic photoredox, copper and chiral phosphoric acid catalysis

作者：Tengfei Xiao, Ke-Rui Jian, Yu‐Cheng Gu, Guo‐Qiang Xu, Peng‐Fei Xu · 发表于：Chemical Science · 年份：2025 · DOI：10.1039/d5sc06987d · 被引用次数：3 · 研究领域：Radical Photochemical Reactions、Catalytic C–H Functionalization Methods、Synthesis and Catalytic Reactions

Existing strategies are typically limited to modifying a C-H site (α or β-position) of saturated cyclic amines, but the asymmetric difunctionalization of vicinal C-H bonds remains a formidable challenge. To address this challenge, this work introduces a synergistic catalytic system that merges visible-light photocatalysis with asymmetric copper and chiral phosphoric acid catalysis. This system enables the enantioselective synthesis of ring-fused amine skeletons by activating vicinal C-H bonds in straightforward saturated cyclic amines. The reaction proceeds in good yields (up to 76%) and excellent enantioselectivity (up to 92% ee). This work describes detailed mechanistic studies that identify the specific dual chiral catalytic system that forms the basis for the enantioselectivity.