Practical Access to Aromatic Thiocyanates by CuCN-Mediated Direct Aerobic Oxidative Cyanation of Thiophenols and Diaryl Disulfides

International audienceThe practical and mild aerobic oxidative CuCN-mediated cyanation of thiophenols and diaryl disulfides was investigated. The reaction was performed in air at room temperature and reached aromatic thiocyanates in moderate to good yields starting from a broad range of diversely functionalized substrates

Intramolecular inverse electron-demand [4+2] cycloadditions of ynamidyl-tethered pyrimidines: Comparative studies in trifluorotoluene and sulfolane

International audienceThree representative 6,7-dihydro-5H-cyclopenta[b]pyridin-4-amines were synthesized using an intramolecular inverse electron demand heteroeDielseAlder/retroeDielseAlder sequence between pyrimidines (acting as azadienes) and ynamides (acting as dienophiles). Two solvents of this reaction, sulfolane and trifluorotoluene, were compared at 210 C and the former consistently led to higher yields. In addition, these studies confirmed the importance of the steric bulk of the C5-position of the pyrimidinyl cycloaddition precursor

Comparative study on the reactivity of propargyl and alkynyl sulfides in palladium-catalyzed domino reactions

International audienceThree types of sulfides bearing a propargyl or an alkynyl moiety have been studied in cyclocarbopalladation/cross-coupling domino palladium-catalyzed sequences. The reactivity of different types of sulfured starting materials has been compared as well as the difference in behavior of these compounds depending on the type of cross coupling ending the domino sequence. It appeared that these cascades were constantly more efficient on the propargyl benzyl thioether. In addition, it has been demonstrated that domino sequences ending with Stille, SuzukieMiyaura, or MizorokieHeck lead efficiently and selectively to the desired cyclized products. Notably, when the introduction of an alkyne is targeted at the end of the cascade, it appeared that the Sonogashira coupling leads every time to the desired cyclic product in the mixture with the product resulting from the direct coupling between the aryl moiety of the substrate and the alkyne used as partner. Finishing the domino sequence with a Stille coupling instead of a Sonogashira one allowed improving significantly the ratio of the mixture in favor of the desired cyclized compound

Aerobic Copper-Mediated Domino Three-Component Approach to 2-Aminobenzothiazole Derivatives

An unprecedented three-component reaction involving a 2,2′-diaminodiaryl disulfide, copper cyanide, and an electrophile is described. This transformation is based on an oxidative copper-mediated S-cyanation as a key step and involves a cyanation/cyclization/acylation domino sequence enabling a rapid and efficient synthesis of diversely substituted 2-aminobenzothiazole derivatives. Notably, this reaction proceeds via an original mechanism involving an intermolecular migration of the acyl group

Supplementary data for the article: Ristić, P.; Todorović, T. R.; Blagojević, V.; Klisurić, O. R.; Marjanović, I.; Holló, B. B.; Vulić, P.; Gulea, M.; Donnard, M.; Monge, M.; Rodríguez-Castillo, M.; López-de-Luzuriaga, J. M.; Filipović, N. R. 1D and 2D Silver-Based Coordination Polymers with Thiomorpholine-4-Carbonitrile and Aromatic Polyoxoacids as Coligands: Structure, Photocatalysis, Photoluminescence, and TD-DFT Study. Crystal Growth & Design 2020, 20 (7), 4461–4478. https://doi.org/10.1021/acs.cgd.0c00287

Supplementary material for: [https://pubs.acs.org/doi/10.1021/acs.cgd.0c00287#]Related to published version: [https://cherry.chem.bg.ac.rs/handle/123456789/4200]Related to accepted version: [https://cherry.chem.bg.ac.rs/handle/123456789/4203

1D and 2D Silver-Based Coordination Polymers with Thiomorpholine-4-carbonitrile and Aromatic Polyoxoacids as Coligands: Structure, Photocatalysis, Photoluminescence, and TD-DFT Study

Four silver-based coordination polymers, {[Ag(L)2](BF4)}∞ (1), {[Ag(H2BTC)(L)]·(H3BTC)}∞ (2), {[Ag2(H2BTEC)(L)2]·3.33H2O}∞ (3), and [Ag(H25SSA)(L)]∞ (4), were synthesized using thiomorpholine-4-carbonitrile (L) as the primary ligand and three aromatic polyoxoacids as coligands: trimesic (H3BTC), pyromellitic (H4BTEC), and 5-sulfosalicylic acid (H35SSA). Compounds 1 and 3 are two-dimensional, while 2 and 4 are one-dimensional. L acts as a bis-monodentate ligand, while the Ag(I) ion is three-coordinated in 2 and four-coordinated in all of the other compounds. The tetrahedral coordination of Ag(I) in 3 leads to an almost complete absence of intermolecular interactions with the metal center. All compounds show reasonable photocatalytic activity for photocatalytic degradation of mordant blue 9 dye, with reaction rates in the 0.036–0.056 min–1 range. Changes in the reaction rates can be correlated with the type and coordination of the coligand. Complex 3 exhibits photoluminescence at 77 K, while 4 exhibits photoluminescence at both room temperature and 77 K. Luminescence lifetimes indicate electronic transitions of singlet parentage, where transitions are allowed. A TD-DFT study determined the contributions of individual singlet–singlet electronic excitations to the fluorescence, indicating that metal– intraligand transitions are responsible for luminescence in both complexes.This is the peer-reviewed version of the article: Ristić, P., Todorović, T.R., Blagojević, V., Klisurić, O.R., Marjanović, I., Holló, B.B., Vulić, P., Gulea, M., Donnard, M., Monge, M., Rodríguez-Castillo, M., López-de-Luzuriaga, J.M., Filipović, N.R., 2020. 1D and 2D Silver-Based Coordination Polymers with Thiomorpholine-4-carbonitrile and Aromatic Polyoxoacids as Coligands: Structure, Photocatalysis, Photoluminescence, and TD-DFT Study. Crystal Growth & Design 20, 4461–4478. [https://doi.org/10.1021/acs.cgd.0c00287]Supplementary material: [https://hdl.handle.net/21.15107/rcub_dais_9452

Nouvelles Métathèses avec Réarrangement de Cycles : Application à la Synthèse d'Oligosaccharides Rares

This work describes a new method for the synthesis of polyunsaturated-polysaccharides The synthesis relies on a ring-rearrangement metathesis (RRM) key step using a RCM-ROM-RCM sequence. Thus, trienic compounds containing a 5- or 6- membered ring as relay moiety allowed us to synthesise several 1,6-linked disaccharides. The method was extended to the synthesis of a trisaccharide via RRM of a tetraenic precusor, featuring two cyclic, relay moieties. This is the first reported example of a synthetically useful efficient RCM-ROM-RCM-ROM-RCM sequence.Ce travail présente une nouvelle voie d'accès aux polysaccharides polyinsaturés via une étape clé de réarrangement de cycle par métathèse (Rn de type RCM-ROM-RCM). En effet au départ de composés triéniques comportant un relais central sous forme d'un cycle à 5 ou 6 chaînons, la synthès de disaccharides liés de manière 1,6 et diversement fonctionnalisés à été réalisée. De même, la synthèse de disaccharides triinsaturés au départ d'un composé tétraénique comportant deux relais cycliques à été réalisée via cette méthode. Au cours de ce travail, nous avons également mis en évidence le premier enchaînement RCM-ROM-RCM-ROM-RCM efficace de la littérature

Nouvelles Métathèses avec Réarrangement de Cycles : Application à la Synthèse d Oligosaccharides Rares

Ce travail présente une nouvelle voie d'accès aux polysaccharides polyinsaturés via une étape clé de réarrangement de cycle par métathèse (Rn de type RCM-ROM-RCM). En effet au départ de composés triéniques comportant un relais central sous forme d'un cycle à 5 ou 6 chaînons, la synthès de disaccharides liés de manière 1,6 et diversement fonctionnalisés à été réalisée. De même, la synthèse de disaccharides triinsaturés au départ d'un composé tétraénique comportant deux relais cycliques à été réalisée via cette méthode. Au cours de ce travail, nous avons également mis en évidence k premier enchaînement RCM-ROM-RCM-ROM-RCM efficace de la littérature.This work describes a new method for the synthesis of polyunsaturated-polysaccharides The synthesis relies on a ring-rearrangement metathesis (RRM) key step usnrg a RCM-ROM-RCM sequence. Thus, trienic compounds containing a 5- or 6- membered ring as relay moiety allowed us to synthesise several 1,6-linked disaccharides. The method was extended to the synthesis of a trisaccharide via RRM of a tetraenic precusor, featuring tw< cyclic, relay moieties. This is the first reported example of a synthetically useful efficient RCM-ROM-RCM-ROM-RCM sequence.MULHOUSE-SCD Sciences (682242102) / SudocSudocFranceF