Mechanochemical Solvent‐Free Catalytic C−H Methylation. Issue 12 (17th December 2020)

• Record Type: Journal Article
• Authors: Ni, Shengjun; Hribersek, Matic; Baddigam, Swarna K.; Ingner, Fredric J. L.; Orthaber, Andreas; Gates, Paul J.; Pilarski, Lukasz T.
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 12(2021)
• Page Start: 6660
• Page End: 6666
• Publication Date: 2020-12-17
• Subjects: arenes -- C−H functionalization -- mechanochemistry -- organometallics -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202010202
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The mechanochemical, solvent‐free, highly regioselective, rhodium‐catalyzed C−H methylation of (hetero)arenes is reported. The reaction shows excellent functional‐group compatibility and is demonstrated to work for the late‐stage C−H methylation of biologically active compounds. The method requires no external heating and benefits from considerably shorter reaction times than previous solution‐based C−H methylation protocols. Additionally, the mechanochemical approach is shown to enable the efficient synthesis of organometallic complexes that are difficult to generate conventionally. Abstract : Catalytic C−H methylation proceeds efficiently under solvent‐free, mechanochemical conditions, including the late‐stage functionalization of biologically active substrates and otherwise difficult‐to‐make metalacyclic complexes.