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Herein, we report a general and mild approach to effectively synthesize N-substituted anilines under metal-free conditions using sulfonyl chlorides and amines. Notably, this approach has shown a wide array of functional group tolerance, operational simplicity, and scalability, making it a useful tool for accessing ,-disubstituted anilines and functionalized products.
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http://dx.doi.org/10.1021/acs.joc.5c01125 | DOI Listing |
Chem Commun (Camb)
September 2025
Division of Medicinal and Process Chemistry, CSIR-Central Drug Research Institute, Lucknow-226031, UP, India.
Herein, we report a catalytic, redox-neutral method for the difunctionalization of oxindoles using ketimines derived from anilines and heteronucleophiles. The reaction proceeds through a dearomatization-aromatization strategy a tetra-substituted alkene intermediate stabilized by extended resonance, facilitating the selective formation of 3,3-disubstituted oxindoles with a wide chemical space in good-to-high yields.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
-Disubstituted arenes are important in various fields but difficult to be directly synthesized by classical methods in the case of two electron-donating substituents due to the ,-orientation. Dehydrogenative aromatization from nonaromatic cyclohexenone motifs and nucleophiles via 1,2- and 1,4-addition to produce -disubstituted arenes is promising as the novel process overcoming the intrinsic problems derived from using aromatic compounds as the substrates; however, there are no reports on tandem oxidation involving dehydrogenative aromatization for one-step synthesis via simultaneous 1,2- and 1,4-addition or -phenylenediamine derivative synthesis because of the quite difficult product selectivity control. Here, by utilizing the unique dehydrogenation catalysis of CeO-supported Au nanoparticles, we have developed one-step synthesis of various -phenylenediamine derivatives via selective aerobic dehydrogenative aromatization from cyclohexenone motifs and secondary amines.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
State Key Laboratory of Advanced Chemical Power Sources, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China.
In organic reactions, controlling the degree of substitution, such as monosubstitution or disubstitution, typically necessitates the use of varied reagents, reaction conditions, and temperatures, often leading to increased separation costs. Simplifying this complexity while developing more direct and efficient methods for controlling reaction outcomes remains a long-standing challenge. In this work, we present a novel and efficient electrochemical strategy that leverages the precise control of electrode potential to selectively halogenate aniline derivatives, offering a breakthrough in the reaction selectivity.
View Article and Find Full Text PDFJ Org Chem
August 2025
Department of Pharmaceutical Technology (Process Chemistry), National Institute of Pharmaceutical Education and Research, S. A. S. Nagar, Punjab 160062, India.
Herein, we report a general and mild approach to effectively synthesize N-substituted anilines under metal-free conditions using sulfonyl chlorides and amines. Notably, this approach has shown a wide array of functional group tolerance, operational simplicity, and scalability, making it a useful tool for accessing ,-disubstituted anilines and functionalized products.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Department of Chemical and Pharmaceutical Biology, Groningen Research Institute of Pharmacy, University of Groningen, Antonius Deusinglaan 1, Groningen, 9713 AV, The Netherlands.
Optically pure N-functionalized α-amino acids are valuable chiral building blocks for pharmaceuticals, nutraceuticals, and agrochemicals. Ethylenediamine-N,N-disuccinic acid lyase from Chelativorans sp. BNC1 catalyzes the addition of a wide range of aliphatic and aromatic primary amines to fumarate, producing the corresponding enantioenriched N-substituted L-aspartic acids.
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