Sulfondiimines are aza-analogues of sulfones and sulfoximines. In contrast to the latter two compound classes, sulfondiimines are rare in the chemical literature. Although a full understanding of the stability and reactivity of sulfondiimines is wanting, sulfondiimines have recently been recognized as novel bioisosteres for carbonyl moieties enabling expansion of the well-known portfolio of pharmaceutically relevant compounds. In this review, we briefly summarize the structure and stability of sulfondiimines and then focus on syntheses and derivatisations of these interesting compounds with sulfur-nitrogen core units. Furthermore, their use in heterocyclic chemistry and recent applications as bioactive compounds are presented.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/d2cs00098a | DOI Listing |
Angew Chem Int Ed Engl
October 2024
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.
Sulfur functional groups are ubiquitous in molecules used in the pharmaceutical and agrochemical industries, and within these collections sulfones hold a prominent position. The double aza-analogues of sulfones, sulfondiimines, offer significant potential in discovery chemistry but to date their applications have been limited by the lack of convenient synthetic routes. The existing methods mainly rely on imination of low-valent-sulfur intermediates, or the combination of pre-formed organometallic reagents and electrophilic S(VI)-functionalities.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.
A modular synthesis of sulfondiimidoyl fluorides-the double aza-analogues of sulfonyl fluorides-allowing variation of the carbon and both nitrogen-substituents is reported. The chemistry uses readily available organometallic reagents, commercial sulfinylamines, simple electrophiles, and N-fluorobenzenesulfonimide (NFSI), as the starting materials. The reactions are broad in scope, efficient, and scalable.
View Article and Find Full Text PDFJ 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 PDFAngew Chem Int Ed Engl
March 2024
Chemistry Department, University of British Columbia, 2036 Main Mall, V6T 1Z1, Vancouver, B.C., Canada.
Sulfilimines, as potential aza-isosteres of sulfoxides, are valued as building blocks, auxiliaries, ligands, bioconjugation handles, and as precursors to versatile S(VI) scaffolds including sulfoximines and sulfondiimines. Here, we report a thioether imination methodology that exploits O-(diphenylphosphinyl)hydroxyl amine (DPPH). Under mild, metal-free, and biomolecule-compatible conditions, DPPH enables late-stage S-imination on peptides, natural products, and a clinically trialled drug, and shows both excellent chemoselectivity and broad functional group tolerance.
View Article and Find Full Text PDFOrg Lett
December 2023
Research Center for Chemical Biology and Omics Analysis, Department of Chemistry, Southern University of Science and Technology, 1088 Xueyuan Boulevard, Shenzhen, Guangdong 518055, P. R. China.
Sulfondiimines, which are isoelectronic with sulfones and sulfoximines, represent a neglected yet intriguing pharmacophore in the discovery program. Herein, we present a facile and mild photocatalytic anti-Markovnikov hydroamination of styrenes for the construction of -alkylated sulfondiimines with primary, secondary, and tertiary alkyl substituents. A sulfondiimine-derived analogue of the marketed drug Vioxx was synthesized using this method as the key step.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!