In this study, a modular approach toward cyclic sulfoximines and sulfondiimines via palladium-catalyzed intramolecular C-H/C-C activation reactions was reported. Various 1,2-benzothiazines including bicyclic, tricyclic, highly fused ones, ones of the seven-membered ring, along with 1,2-benzothiazine 1-imines were accessed in good yields. KIE experiment demonstrated that the C-H bond cleavage at the position to the sulfoximine group is not the rate-determining step in the coupling reaction.
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http://dx.doi.org/10.1021/acs.joc.3c02799 | DOI Listing |
Pharmazie
August 2024
Institute of Pharmacy, University of Greifswald, Germany.
The present work reports on the preparation of the hitherto unknown title compounds with various synthetic routes described. The initially pursued concept of S-N exchange with varioius 1-substituted 3-methylsulfanyl-5,6,7,8-tetrahydro-1 -[1,2,4]triazolo[1,2- ]pyridazines by using nitrogen nucleophiles was only marginally successful. The reactions proceeded slowly and the yields were low, mainly because of the pronounced formation of 5,6,7,8-tetrahydro-[1,2,4]triazolo[1,2- ]pyridazin-1-imines by oxidation of the heterocyclic amines initially formed.
View Article and Find Full Text PDFOrg Biomol Chem
May 2024
Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, China.
J Org Chem
March 2024
Guangxi Key Laboratory of Natural Polymer Chemistry and Physics, College of Chemistry and Materials, Nanning Normal University, Nanning 530001, P. R. China.
In this study, a modular approach toward cyclic sulfoximines and sulfondiimines via palladium-catalyzed intramolecular C-H/C-C activation reactions was reported. Various 1,2-benzothiazines including bicyclic, tricyclic, highly fused ones, ones of the seven-membered ring, along with 1,2-benzothiazine 1-imines were accessed in good yields. KIE experiment demonstrated that the C-H bond cleavage at the position to the sulfoximine group is not the rate-determining step in the coupling reaction.
View Article and Find Full Text PDFChem Asian J
November 2023
Department of Chemistry, SRM University AP, Amaravati, Andhra Pradesh, 522502, India.
A palladium-catalyzed denitrogenative transannulation strategy to access various 3-substituted isocoumarin-1-imine frameworks using 1,2,3-benzotriazin-4(3H)-ones and terminal alkynes is described. The reaction is highly regioselective and tolerates a wide range of functional groups. The reaction is believed to proceed via a five-membered palladacycle intermediate extruding environmentally benign molecular nitrogen as a by-product.
View Article and Find Full Text PDFChem Commun (Camb)
August 2023
Fluoro-Agrochemicals Division, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Tarnaka, Hyderabad, Telangana 500007, India.
Merging C(sp)-H allylation and alkene difunctionalization events to access isochroman-1-imines, using -aroyl aminoesters, MBH acetates, and NBS, under Ru(II)/Ru(IV) catalysis has been developed. Using H NMR, ESI-MS, HRMS, control reactions, deuterium labeling experiments, and DFT analysis, the allyl transfer (redox) process was proven to involve in C-H allylation rather than olefin insertion. Scale-up and synthetic transformations demonstrated the sustainability of this method.
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