Iodine-DMSO mediated conversion of <i>N</i>-arylcyanothioformamides to <i>N</i>-arylcyanoformamides and the unexpected formation of 2-cyanobenzothiazoles

Moussa, Ziad; Judeh, Zaher M. A.; Alzamly, Ahmed; Ahmed, Saleh A.; Al‐Masri, Harbi Tomah; al‐Hindawi, Bassam; Rasool, Faisal; Saada, Sara

doi:10.1039/d2ra00049k

Cited by 6 publications

(9 citation statements)

References 84 publications

(77 reference statements)

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“…Thus, pursuing this idea, several variously substituted N -arylcyanothioformamides 27a–x ( Scheme 2 a) were prepared on 20 mmol scale from commercial isothiocyanates 26a–x and potassium cyanide in water-ethanol in good yields (65–88%) ( Scheme 2 ). The physical and spectral data of 27a–x matched those reported in the literature [ 33 ]. Preparation of the hydrazonoyl chlorides coupling partners 29a–m ( Scheme 2 b) was carried out according to literature methods described previously [ 34 , 35 ].…”

Section: Resultssupporting

confidence: 75%

First X-ray Crystal Structure Characterization, Computational Studies, and Improved Synthetic Route to the Bioactive 5-Arylimino-1,3,4-thiadiazole Derivatives

Moussa

Paz

Judeh

et al. 2023

IJMS

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N-arylcyanothioformamides are useful coupling components for building key chemical intermediates and biologically active molecules in an expedited and efficient manner. Similarly, substituted (Z)-2-oxo-N-phenylpropanehydrazonoyl chlorides have been utilized in numerous one-step heteroannulation reactions to assemble the structural core of several different types of heterocyclic compounds. Herein, we demonstrate the effectiveness of the reaction of N-arylcyanothioformamides with various substituted (Z)-2-oxo-N-phenylpropanehydrazonoyl chlorides to produce, stereoselectively and regioselectively, a range of 5-arylimino-1,3,4-thiadiazole derivatives decorated with a multitude of functional groups on both aromatic rings. The synthetic methodology features mild room-temperature conditions, large substrate scope, wide array of functional groups on both reactants, and good to high reaction yields. The products were isolated by gravity filtration in all cases and structures were confirmed by multinuclear NMR spectroscopy and high accuracy mass spectral analysis. Proof of molecular structure of the isolated 5-arylimino-1,3,4-thiadiazole regioisomer was obtained for the first time by single-crystal X-ray diffraction analysis. Crystal-structure determination was carried out on (Z)-1-(5-((3-fluorophenyl)imino)-4-(4-iodophenyl)-4,5-dihydro-1,3,4-thiadiazol-2-yl)ethan-1-one and (Z)-1-(4-phenyl-5-(p-tolylimino)-4,5-dihydro-1,3,4-thiadiazol-2-yl)ethan-1-one. Similarly, the tautomeric structures of the N-arylcyanothioformamides and (Z)-geometries of the 2-oxo-N-phenylpropanehydrazonoyl chloride coupling partners were proven by X-ray diffraction studies. As representative examples, crystal-structure determination was carried out on (4-ethoxyphenyl)carbamothioyl cyanide and (Z)-N-(2,3-difluorophenyl)-2-oxopropanehydrazonoyl chloride. Density functional theory calculations at the B3LYP-D4/def2-TZVP level were carried out to rationalize the observed experimental findings.

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Section: Resultssupporting

confidence: 75%

First X-ray Crystal Structure Characterization, Computational Studies, and Improved Synthetic Route to the Bioactive 5-Arylimino-1,3,4-thiadiazole Derivatives

Moussa

Paz

Judeh

et al. 2023

IJMS

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“…Some compounds of the 4 series ( 4a , 4b , 4f , 4o , 4i , 4k , 4l , 4n , 4p , 4r , 4u and 4af ) were randomly described in studies cited in this paper [ 44 , 47 , 48 , 51 , 57 , 69 ]. To complete data sometimes uneasy to find in the literature, all compounds 4 were fully characterized.…”

Section: Methodsmentioning

confidence: 99%

“… Synthesis of 2-cyanated benzothiazoles from 5- N -arylimino-4-chloro-1,2,3-dithiazoles and N -arylcyanothioformamides and description of the present work. References involved in these studies: [ 47 , 48 , 51 , 52 , 55 , 57 ]. …”

Section: Figure Schemes and Tablesmentioning

confidence: 99%

“… 1 Isolated yield. Compounds described in 2 [ 48 ]; 3 [ 47 ]; 4 [ 50 ]; 5 [ 64 ]; 6 [ 57 ]; 7 [ 17 ]; 8 [ 65 ]; 9 [ 66 ]; 10 [ 67 ]. …”

Section: Figure Schemes and Tablesmentioning

confidence: 99%

“…Benzothiazole ring closure was performed with palladium chloride (PdCl 2 ) and copper iodide (CuI) as catalysts with tetrabutylammonium bromide (TBAB) as an organic additive, in a mixture of DMSO/DMF (1:1, v / v ) as the solvent [ 55 , 56 ]. Recently, Moussa et al investigated the efficiency of I 2 -DMSO as an oxidative system and described the unexpected conversion of some N -arylcyanothioformamides into 2-cyanobenzothiazoles (five examples, Figure 1 ) [ 57 ].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of 2-Cyanobenzothiazoles via Pd-Catalyzed/Cu-Assisted C-H Functionalization/Intramolecular C-S Bond Formation from N-Arylcyanothioformamides

et al. 2022

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We report herein on a catalytic system involving palladium and copper to achieve the cyclization of N-arylcyanothioformamides and the synthesis of 2-cyanobenzothiazoles. The C-H functionalization/intramolecular C-S bond formation reaction was achieved in the presence of air, using 2.0 equiv of an inorganic additive (KI). In many cases, the reaction led to a sole product regioselectively obtained in good yields, allowing the synthesis of a wide range of substituted 2-cyanobenzothiazole derivatives, providing valuable building blocks for the design of more complex heterocyclic or molecular labeling systems.

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Sulfur‐ and Amine‐ Promoted Multielectron Autoredox Transformation of Nitromethane: Multicomponent Access to Thiourea Derivatives

Phaenok,

Nguyen,

Soorukram

et al. 2023

Chemistry A European J

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Thiourea derivatives are in‐demand motifs in organic synthesis, medicinal chemistry and material science, yet redox methods for the synthesis that start from safe, simple, inexpensive and readily available feedstocks are scarce. In this article, we disclose the synthesis of these motifs using elemental sulfur and nitromethane as the starting materials. The method harnesses the multi‐electron auto‐redox property of nitromethane in the presence of sulfur and amines, delivering thiourea products without any added oxidant or reductant. Extension of this reaction to cyclizable amines and/or higher homologues of nitromethane led to a wide range of nitrogen heterocycles and thioamides. Operationally simple, the reactions are scalable, tolerate a wide range of functional groups, and can be employed for the direct functionalization of natural products. Mechanistically, the nitro group was found to act as an oxidant leaving group, being reduced to ammonia whereas sulfur, along with the role of a sulfur building block for the thiocarbonyl group, behaved as a complementary reductant, being oxidized to sulfate.

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Iodine-DMSO mediated conversion of N-arylcyanothioformamides to N-arylcyanoformamides and the unexpected formation of 2-cyanobenzothiazoles

Abstract: Conversion of N-arylcyanothioformamides to N-arylcyanoformamides and 2-cyanobenzothiazoles has been achieved with I2-DMSO oxidative system.

Cited by 6 publications

References 84 publications

First X-ray Crystal Structure Characterization, Computational Studies, and Improved Synthetic Route to the Bioactive 5-Arylimino-1,3,4-thiadiazole Derivatives

First X-ray Crystal Structure Characterization, Computational Studies, and Improved Synthetic Route to the Bioactive 5-Arylimino-1,3,4-thiadiazole Derivatives

Synthesis of 2-Cyanobenzothiazoles via Pd-Catalyzed/Cu-Assisted C-H Functionalization/Intramolecular C-S Bond Formation from N-Arylcyanothioformamides

Sulfur‐ and Amine‐ Promoted Multielectron Autoredox Transformation of Nitromethane: Multicomponent Access to Thiourea Derivatives

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