Light-Promoted Dearomative Amination of Nonactivated Arenes via Redox-Neutral Chromium-Nitrenoid Transfer
Hui Xie1, Wei-Long Zeng1, Chu-Qiao Li1
1State Key Laboratory of Soil Pollution Control and Safety, Department of Chemistry, Zhejiang University, Hangzhou310058, China.
Abstract:
A light-driven dearomative amination of nonactivated arenes via redox-neutral Cr-nitrenoid transfer is reported. We designed a novel Cr(0) redox-neutral mode that overcomes traditional Cr(0)/Cr(II) redox pathways in dearomatization chemistry using (η6-arene)Cr(CO)3, thereby shifting the electrophile scope from obligatory cationic species to neutral nitrenes for the first time. This strategy enables both dearomative 1,2-hydroamination and 1,2-carboamination with exclusive regio- and stereocontrol, broad functional-group tolerance, and preferential site-selectivity for benzene rings over heteroarenes.
Related Concept Videos
Preparation of Amines: Reductive Amination of Aldehydes and Ketones
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
Radical Formation: Addition
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an unpaired...
Nitriles to Amines: LiAlH4 Reduction
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...


![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)