Accessing fascinating organic and biological significant indolines via dearomatization of indoles represents one of the most efficient approaches. However, it has been difficult for the dearomatization of the electron deficient indoles. Here we report the studies leading to developing a photoredox mediated Giese-type transformation strategy for the dearomatization of the indoles. The reaction has been implemented for chemoselectively breaking indolyl C=C bonds embedded in the aromatic system. The synthetic power of this strategy has been demonstrated by using structurally diverse indoles bearing common electron-withdrawing groups including (thio)ester, amide, ketone, nitrile and even aromatics at either C₂ or C₃ positions and ubiquitous carboxylic acids as radical coupling partner with high trans-stereoselectivity (>20:1 dr). This manifold can also be applied to other aromatic heterocycles including pyrroles, benzofurans and benzothiophenes. Furthermore, enantioselective dearomatization of indoles has been achieved by a chiral camphorsultam auxiliary with high diastereoselectivity.

通过吲哚的脱芳构化获得令人着迷的有机和生物重要的吲哚啉是最有效的方法之一。然而，缺电子吲哚的脱芳构化一直很困难。在这里，我们报告了开发光氧化还原介导的用于吲哚脱芳构化的吉斯型转化策略的研究。该反应已用于化学选择性地破坏芳香系统中嵌入的吲哚基 C=C 键。该策略的合成能力已通过使用具有常见吸电子基团（包括（硫代）酯、酰胺、酮、腈甚至 C 2 或 C 3 位芳香族化合物）的结构多样的吲哚和普遍存在的羧酸作为自由基偶联_伴侣来_证明。具有高反式立体选择性（>20:1 dr）。该流形也可应用于其他芳香杂环，包括吡咯、苯并呋喃和苯并噻吩。此外，通过具有高非对映选择性的手性樟脑磺内酰胺助剂实现了吲哚的对映选择性脱芳构化。