The selective oxidation of amines into imines is a priority research topic in organic synthesis and has attracted much attention over the past few decades. However, the oxidation of amines generally suffers from the drawback of transition-metal, even noble-metal catalysts. Thus, the strategy of metal- and oxidant-free selective synthesis of imines is highly desirable yet largely unmet. This paper unravels a metal-free and external oxidant-free electrochemical strategy for the oxidative coupling methodology of amines. This general transformation is compatible with various functional amines and led to functionalized imines in moderate to satisfactory yields.
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http://dx.doi.org/10.1039/d1ra07263c | DOI Listing |
Org Lett
January 2025
Innovation Center for Chemical Sciences, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou Industrial Park, Suzhou, Jiangsu 215123, China.
Herein, visible-light-induced annulation of benzothioamides with sulfoxonium ylides to furnish thiazole derivatives is developed under transition-metal-, photocatalyst-, and oxidant-free conditions. This protocol exhibits good substrate scope, affording the desired products with satisfied yields in a mild and green manner. Detailed mechanistic studies suggest that the benzothioamide substrate plays a dual role in this reaction.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
Hefei National Research Center for Physical Sciences at Microscale, Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China.
An electrochemical synthesis of various nitroso organic compounds (NOCs) from secondary amines was developed under metal-free and oxidant-free conditions. This method used commercially available nitromethane as the nitrosation reagent to provide various NOCs in good to excellent yields. Furthermore, the valuable drug molecule form desloratadine can be prepared by this method easily.
View Article and Find Full Text PDFJ Org Chem
December 2024
Green Pharmaceutical Technology Key Laboratory of Luzhou City, School of Pharmacy, Southwest Medical University, Luzhou, Sichuan 646000, P. R. China.
A cerium-catalyzed C-H alkylation of -sulfonyl ketimines with low-cost and readily available alkanes as alkyl sources was developed. This transformation proceeded through the synergy of photoinitiated ligand-to-metal charge transfer (LMCT) using a chlorine radical as an HAT reagent and air as a green oxidant. A series of alkylated -sulfonyl ketimines were synthesized with moderate to good yields in a highly atom-economic manner under chemical oxidant-free conditions.
View Article and Find Full Text PDFJ Org Chem
December 2024
Yunnan Key Laboratory of Modern Separation Analysis and Substance Transformation, College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming Yunnan Province 650500, P. R. China.
Visible light-promoted α-aminoalkyl radical-triggered α-aminoalkylation and α-diaminoalkylation of Morita-Baylis-Hillman acetates with -methyl arylamines to synthesize -containing alkyl acrylates and γ,γ-diaminobutyl esters was reported. Photoinduced α-aminoalkylation is carried out with Na-eosin Y as an organophotocatalyst at room temperature under metal- and oxidant-free conditions. In particular, the α-diaminoalkylation is performed via α-aminoalkyl radical addition/elimination followed by a catalyst-controlled selective α-aminoalkyl radical addition strategy in one step under the [Ir(dtbbpy)(bpy))]PF/KF catalytic system.
View Article and Find Full Text PDFOrg Lett
November 2024
Key Laboratory of Green and Precise Synthetic Chemistry and Application, Ministry of Education, Anhui Provincial Key Laboratory of Synthetic Chemistry and Applications, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei, Anhui 235000, P. R. China.
A novel chemoselective Brook-oxidation reaction of acylsilanes initiated by the carbamoyl anion has been successfully developed for the first time. This method enables the synthesis of diverse α-ketoamides and α-ketothioamides under transition metal-free and strong oxidant-free conditions with high yields and high chemoselectivity. It also demonstrates tolerance toward a wide range of functional groups.
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