Polythioamide is a unique type of sulfur-containing polymer with advanced functionalities. Nonetheless, the elemental sulfur commonly used in their synthesis tends to react readily with unsaturated functional groups, thereby limiting the scope of eligible substrates. Inspired by the highly efficient sulfur-fluoride exchange (SuFEx) polymerization through discrete hubs, we present herein a pioneering and versatile approach to the synthesis of polythioamides from diboronic acids, secondary diamines, and thiocarbonyl fluoride as the central connective hub. Well-defined structures, including previously inaccessible unsaturated substrates, were realized. These newly devised polythioamides can efficiently and selectively bind to metal ions and were applied in precious-metal recovery. Further development resulted in Pd -crosslinked single-chain nanoparticles serving as recyclable homogeneous catalysts, thus demonstrating the vast potential of these unprecedented polythioamides. We anticipate that thiocarbonyl fluoride could emerge as a potent hub for facilitating the intricate synthesis of sulfur-containing polymers.
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http://dx.doi.org/10.1002/anie.202313779 | DOI Listing |
Angew Chem Int Ed Engl
November 2023
School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China.
Polythioamide is a unique type of sulfur-containing polymer with advanced functionalities. Nonetheless, the elemental sulfur commonly used in their synthesis tends to react readily with unsaturated functional groups, thereby limiting the scope of eligible substrates. Inspired by the highly efficient sulfur-fluoride exchange (SuFEx) polymerization through discrete hubs, we present herein a pioneering and versatile approach to the synthesis of polythioamides from diboronic acids, secondary diamines, and thiocarbonyl fluoride as the central connective hub.
View Article and Find Full Text PDFAcc Chem Res
June 2023
Department of Chemistry and Biochemistry, Jackson State University, 1400 J. R. Lynch Street, Jackson, Mississippi 39217, United States.
ConspectusOver the past five decades, significant progress has been made in the field of anion recognition with a diverse variety of synthetic receptors because of the fundamental importance of anions in chemical, environmental, and biological processes. In particular, urea- and thiourea-based molecules offering directional binding sites are attractive receptors for anions due to their ability to bind anions employing primarily hydrogen-bonding interactions under neutral conditions and have gained a recent paramount attention in the area of supramolecular chemistry. The presence of two imine (-NH) groups on each urea/thiourea functionality in these receptors gives them potential for excellent binding of an anion, mimicking the natural binding process in living cells.
View Article and Find Full Text PDFChem Commun (Camb)
July 2019
School of Chemical Engineering, Nanjing University of Science and Technology, 200 Xiao Ling Wei Street, Nanjing 210094, China.
A newly developed CF3SO2Na-based trifluoromethylation of secondary amines has been disclosed, and the method has been successfully extended to the configuration of perfluoroalkyl amines using RfSO2Na, complementing the established synthesis strategy of trifluoromethyl amines. Advantages of the method include good functional group tolerance, mild conditions, and inexpensive or easy-to-handle materials. Mechanistic probes indicate that the thiocarbonyl fluoride formed in situ is the key intermediate in the reaction.
View Article and Find Full Text PDFOrg Lett
April 2019
School of Chemistry and Molecular Engineering , East China Normal University, 500 Dongchuan Road , Shanghai 200241 , China.
Org Lett
October 2018
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry , Fuzhou University, Fujian 350108 , China.
A one-pot strategy for the diversified synthesis of 3-difluoromethyl benzoxazole-2-thiones is reported. The reaction of 2-aminophenol, sodium chlorodifluoroacetate, and elemental sulfur in the presence of NaO t-Bu gives exclusively 3-difluoromethyl benzoxazole-2-thiones in good yield (up to 98%). The mechanism of this reaction presumably involves first cyclization of 2-aminophenols with thiocarbonyl fluoride, followed by N-difluoromethylation with difluorocarbene.
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