CuBr-ZnI2 Combo-Catalysis for Mild CuI-CuIII Switching and sp2 C-H Activated Rapid Cyclization to Quinolines and Their Sugar-Based Chiral Analogues: A UV-Vis and XPS Study.

Abstract

An unprecedented CuBr–ZnI2 combo-catalyzed mild Cu1–CuIII switching activation of sp2 C–H of highly electron-rich arenes is reported. Anilines, aldehydes, and terminal alkynes were rapidly coupled together at ambient temperature to construct a ubiquitous quinoline framework through cyclization of the C≡C bond. This smart solvent-free strategy was exploited for the direct synthesis of valuable 4-substituted, 2,4-disubstituted, and thermally labile sugar-based chiral quinolines in good yields. In contrast to the frequently used imine–alkyne cyclization reaction, this uncommonly mild CuI–CuIII combo-catalysis for a rapid three-component cyclization is expected to proceed through the formation of a flexible propargyl amine intermediate, which provides a CuI-procatalyst for rapid sp2 C–H activation with cyclization involving transient CuIII species. The in situ generation of transient CuIII species was confirmed through online ultraviolet–visible spectroscopy (UV–vis), electrospray ionization mass spectrometry (ESI-MS), and X-ray photoelectron spectroscopy (XPS) analyses.