N-(2, 3, 5, 6-Tetrafluoropyridyl)sulfoximines: synthesis, X-ray crystallography, and halogen bonding. Issue 23 (27th October 2020)

• Record Type: Journal Article
• Authors: Schumacher, Christian; Fergen, Hannah; Puttreddy, Rakesh; Truong, Khai-Nghi; Rinesch, Torsten; Rissanen, Kari; Bolm, Carsten
• Is Part Of: Organic chemistry frontiers. Volume 7:Issue 23(2020)
• Page Start: 3896
• Page End: 3906
• Publication Date: 2020-10-27
• Subjects: Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1039/d0qo01139h
• Languages: English
• ISSNs: 2052-4110

Abstract

Abstract : N -(Tetrafluoropyridyl)sulfoximines are obtained from N H-sulfoximines and pentafluoropyridine under solution-based or mechanochemical conditions, and the solid-state structures of 26 products have been determined by X-ray diffraction analysis. Abstract : In the presence of KOH, N H-sulfoximines react with pentafluoropyridine to give N -(tetrafluoropyridyl)sulfoximines ( N TFP-sulfoximines) in moderate to excellent yields. Either a solution-based or a superior solvent-free mechanochemical protocol can be followed. X-Ray diffraction analyses of 26 products provided insight into the bond parameters and conformational rigidity of the molecular scaffold. In solid-state structures, sulfoximines with halo substituents on the S -bound arene are intermolecularly linked by C–X⋯OS (X = Cl, Br) halogen bonds. Hirshfeld surface analysis is used to assess the type of non-covalent contacts present in molecules. For mixtures of three different S -pyridyl-substituted N TFP-sulfoximines and N -iodosuccinimide (NIS) in CDCl3, association constants were determined by 1 H NMR spectroscopy. The data revealed a dependence of the halogen bond strength on the position of the pyridyl nitrogen indicating the presence of N–I⋯N( S -pyridyl) interactions. Neither the SO oxygen nor the tetrafluoropyridyl-substituted nitrogen of the sulfoximine appeared to be involved in halogen bonding.