The cross-coupling of -tosylhydrazones and aryl halides forms carbon-carbon bonds, producing 1,1-disubstituted alkenes. Though it has proven extremely useful in several fields of chemistry, its mechanism remains experimentally unexplored. Combining benchtop NMR and real-time mass spectrometry afforded the ability to monitor the catalytic intermediates as well as the rate of product formation.
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Three-component diels-alder reaction through palladium carbene migratory insertion enabled dearomative C(sp)-H bond activation.
Nat Commun
December 2024
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan, 410081, China.
Owning to the versatile nature in participation of Diels-Alder (D-A) reactions, the development of efficient approaches to generate active ortho-quinodimethanes (o-QDMs) has gained much attention. However, a catalytic method involving coupling of two readily accessible components to construct o-QDMs is lacking. Herein, we describe a palladium carbene migratory insertion enabled dearomative C(sp)-H activation to form active o-QDM species through the cross-coupling of N-tosylhydrazones with aryl halides.
View Article and Find Full Text PDFSadphos as Adaptive Ligands in Asymmetric Palladium Catalysis.
Acc Chem Res
January 2024
Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai, 200433, China.
ConspectusPalladium catalysis, as one of the most important strategies in asymmetric synthesis, has continuously attracted the attention of organic chemists. With the development of chiral ligands, increasingly challenging reactions and substantial progress in asymmetric catalysis are being realized.Since 2014, we have focused on exploiting a series of sulfinamide phosphine ligands called "Sadphos," including Ming-Phos, Xu-Phos, Xiao-Phos, Xiang-Phos, TY-Phos, PC-Phos, GF-Phos, and WJ-Phos.
View Article and Find Full Text PDFSynthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones.
Commun Chem
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Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131, Karlsruhe, Germany.
Tetraphenylethylenes (TPEs) are well-known for their aggregation-induced emission properties. The synthesis of TPE derivatives, as well as other highly substituted olefins, generally requires the use of hazardous reagents, such as metalorganic compounds, to overcome the high activation energies caused by the sterically congested double bond. Herein, we present an efficient and metal-free procedure for the synthesis of tetraarylethylenes via alkylidene-homocoupling of N-tosylhydrazones, derived from readily available benzophenones, in excellent yields.
View Article and Find Full Text PDFRecyclable Copper(I)-Catalyzed Cross-Coupling of Trialkylsilylethynes and -Tosylhydrazones Leading to the Formation of C(sp)-C(sp) Bonds.
J Org Chem
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Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education and College of Chemistry & Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China.
A highly efficient heterogeneous copper(I)-catalyzed cross-coupling of trialkylsilylethynes with -tosylhydrazones has been achieved in dioxane at 90-110 °C via the Cu carbene migratory insertion with an SBA-15-immobilized l-proline-Cu(I) complex [SBA-15-l-Proline-CuI] as the catalyst and LiOBu as the base, leading to the formation of C(sp)-C(sp) bonds. The reaction generates a wide variety of alkyltrialkylsilylalkynes in moderate to high yields. This new heterogenized copper(I) complex exhibits a comparable catalytic efficiency to homogeneous CuI and can be easily recovered through a simple centrifugation process and is recyclable up to 12 times without a remarkable loss of activity.
View Article and Find Full Text PDFCross-Coupling of Cyclobutenone -Tosylhydrazones with Organohalides: Access to Conjugated Enynes and Enallenes via a Strained Allylpalladium Intermediate.
Org Lett
December 2022
West China School of Public Health and West China Fourth Hospital and State Key Laboratory of Biotherapy, Sichuan University, Chengdu 610041, China.
A palladium-catalyzed cross-coupling reaction of cyclobutenone -tosylhadrazones with organohalides is disclosed. The protocol involves the generation of a strained allylpalladium intermediate from readily available starting materials through palladium carbene migratory insertion, which undergoes electrocyclic ring opening and β-hydride elimination for the production of conjugated enynes and enallenes. The broad substrate scope, good to excellent yields, and tunable product diversity make the protocol potentially useful in organic synthesis.
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