Affiliation:
1. School of Natural Science Department Chemie Technische Universität München Lichtenbergstr. 4 Garching bei München 85748 Germany
2. TUM Catalysis Research Center Technische Universität München Ernst-Otto-Fischer-Str. 1 Garching bei München 85748 Germany
Abstract
AbstractSyntheses of (partially) aromatic nitrogen heterocycles increasingly rely on transition‐metal catalyzed C−C‐ and C−N‐cross‐coupling reactions. Here we describe a different approach to the synthesis of indolines by a domino C(sp3)−H activation, 1,2‐addition, and defluorinative SNAr‐cyclization sequence to provide the target 1,2‐diarylindolines (1,2‐diaryl‐2,3‐dihydroindoles) from ortho‐fluorinated methyl‐arenes and N‐aryl imines (benzylidene anilines) in a cyclocondensation that is mediated by potassium hexamethyldisilazide (KHMDS) as base exclusively. This transition‐metal‐free process via C−H and C−F bond activation provides a one‐step entry into a wide array of indoline scaffolds (43 examples, up to 96 % yield). This privileged substructure is common in natural products and pharmaceuticals alike, and cannot be accessed by traditional condensation reactions.