Synthesis of Multisubstituted Benzimidazolones via Copper-Catalyzed Oxidative Tandem C–H Aminations and Alkyl Deconstructive Carbofunctionalization

• Published in: iScience Vol. 15; pp. 127 - 135
• Main Authors: Liang, Taoyuan, Zhao, He, Gong, Lingzhen, Jiang, Huanfeng, Zhang, Min
• Format: Journal Article
• Language: English
• Published: United States Elsevier Inc 31.05.2019; Elsevier
• Subjects: Catalysis; Chemistry; Organic Chemistry; Chemistry; Catalysis; Organic Chemistry
• ISSN: 2589-0042; 2589-0042
• DOI: 10.1016/j.isci.2019.04.019

Benzimidazolone constitutes the core structure of numerous pharmaceuticals, agrochemicals, inhibitors, pigments, herbicides, and fine chemicals. Amination of hydrocarbons is an attractive tool for the creation of nitrogen-containing products. However, the multiple steps, harsh conditions, and low atom efficiencies often present in these reactions remain challenging. We present a multicomponent synthesis of functional benzimidazolones from arylamines, dialkylamines, and alcohols, acting via the sequence of copper-catalyzed oxidative tandem C–H aminations and alkyl deconstructive carbofunctionalization. The catalytic transformation forms multiple bonds in one single operation, uses readily available feedstocks and a naturally abundant Cu/O2 catalyst system, has broad substrate scope, avoids pre-installation of aminating agents and directing groups, and provides high chemo- and regioselectivity, resulting in direct functionalization of inert C–H and C–C bonds via single-electron oxidation-induced activation mode. This platform can be expected to provide structurally diverse products with interesting biological, chemical, and physical properties. [Display omitted] •Tandem C–H aminations•C(sp3)–C(sp3) bond deconstructive carbofunctionalization•Multicomponent synthesis•High chemo- and regioselectivity Chemistry; Catalysis; Organic Chemistry