Synthesis of isothiosemicarbazones of potential antitumoral activity through a multicomponent reaction involving allylic bromides, carbonyl compounds and thiosemicarbazide

Munaretto, Laiéli S.; Ferreira, Misael; Gouvêa, Daniela P.; Bortoluzzi, Adaílton J.; Assunção, Laura Sartori; Inaba, Juliana; Creczynski-Pasa, Tânia Beatriz; Sá, Marcus M.

doi:10.1016/j.tet.2020.131231

Cited by 5 publications

(3 citation statements)

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“… 5 − 8 Even after more than 100 years of research, 9 unprecedented reaction outcomes of these starting materials have still been recently reported. 10 In contrast, isothiosemicarbazonium salts ( IV ; Scheme 1 A)—key intermediates for the preparation of the intensively studied isothiosemicarbazones ( III ) 11 − 16 —were thus far not extensively investigated for their use in cyclization reactions. Merely, their ring—chain tautomerism in solution was studied via NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

“…Thiosemicarbazide ( I ) and the closely related thiosemicarbazones ( II ) and isothiosemicarbazones ( III ) have been synthetically exploited over decades (Scheme A). After early applications in the qualitative analysis of aldehydes and ketones, the applicative focus later shifted toward their use as ligands in coordination chemistry. − Compounds I – III were also soon identified as versatile starting materials in organic synthesis offering four distinct nucleophilic centers and thus allowing cascade reactions to give various heterocyclic compounds. − Even after more than 100 years of research, unprecedented reaction outcomes of these starting materials have still been recently reported . In contrast, isothiosemicarbazonium salts ( IV ; Scheme A)key intermediates for the preparation of the intensively studied isothiosemicarbazones ( III ) − were thus far not extensively investigated for their use in cyclization reactions.…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic Insights into the Formation of 1-Alkylidene/Arylidene-1,2,4-triazolinium Salts: A Combined NMR/Density Functional Theory Approach

et al. 2022

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In a recent report on the synthetic approach to the novel substance class of 1-alkylidene/arylidene-1,2,4-triazolinium salts, a reaction mechanism suggesting a regioselective outcome was proposed. This hypothesis was tested via a combined NMR and density functional theory (DFT) approach. To this end, three experiments with 13 C-labeled carbonyl reactants were monitored in situ by solution-state NMR. In one experiment, an intermediate as described in the former mechanistic proposal was observed. However, incorporation of 13 C isotope labels into multiple sites of the heterocycle could not be reconciled with the “regioselective mechanism”. It was found that an unproductive reaction pathway can lead to 13 C scrambling, along with metathetical carbonyl exchange. According to DFT calculations, the concurring reaction pathways are connected via a thermodynamically controlled cyclic 1,3-oxazetidine intermediate. The obtained insights were applied in a synthetic study including aliphatic ketones and para-substituted benzaldehydes. The mechanistic peculiarities set the potential synthetic scope of the novel reaction type.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into the Formation of 1-Alkylidene/Arylidene-1,2,4-triazolinium Salts: A Combined NMR/Density Functional Theory Approach

et al. 2022

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“…In fact, thiosemicarbazide and its derivatives have interesting biological properties [1][2][3]. Organic molecules obtained from thiosemicarbazide which have shown antioxidant [4,5], antitumor [5,6], antituberculosis [7,8], antifungal [7,9], antibacterial [7,10] or analgesic [11] properties are largely reported in the literature. To improve the properties of these derivatives, many metals transition [12][13][14] and tin complexes [15][16][17] were prepared from these types of Schiff bases.…”

Section: Introductionmentioning

confidence: 99%

Crystal structures of bis[1-(1-hydroxypropan-2-ylidene)thiosemicarbazide-κ3S,N,O)cobalt(III)-tetra(thiocyanato-κN) cobalt(II) methanol solvate, bis{1-(1-hydroxypropan-2-ylidene)thiosemicarbazide-κ3S,N,O}nickel(II) bis(thiocyanate) and (1-(1-hydroxypropan-2-ylidene)thiosemicarbazide-κ3S,N,O)bis(thiocyanato-κN)zinc(II)

et al. 2022

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The reactions of Schiff base 1-(1-hydroxypropan-2-ylidene)thiosemicarbazide (H2L), with salt of thiocyanate metal (II) (Co, Ni, or Zn), provided one dinuclear and two new mononuclear complexes, formulated respectively as {[Co(LH)2]2·[Co(NCS)4] ·2(MeOH)} (1), {[Ni(H2L)2]·[(NCS)2]} (2) and [Zn(H2L)(NCS)2] (3). These compounds have been studied and characterized by elemental analysis, infrared, and ultraviolet-visible (UV-vis) spectroscopies. The structures of the three complexes have been resolved by X-ray crystallography technique. The dinuclear complex 1 crystallizes in the orthorhombic space group Fdd2 with the following unit cell parameters a = 33.1524 (3) Å, b = 19.3780 (2) Å, c = 13.2533 (2) Å, V = 8514.28 (17) Å3, Z = 16, R1 = 0.025 and wR2 = 0.063, the mononuclear complex 2 crystallizes in the monoclinic space group P21/n with the following unit cell parameters a = 11.5752 (1) Å, b = 12.3253 (1) Å, c = 14.2257 (2) Å, β = 106.855 (1)°, V = 1942 (4) Å3, Z = 4, R1 = 0.038 and wR2 = 0.106 and the mononuclear complex 3 crystallizes in the monoclinic space group P21/c with the following unit cell parameters a = 6.1121 (2) Å, b = 26.8272 (7) Å, c = 8.0292 (2) Å, β = 99.876 (3)°, V = 1297.04 (6) Å3, Z = 4, R1 = 0.026 and wR2 = 0.057. The asymmetric unit of Complex 1 contains one cationic unit in which the ligand acts in its monodeprotonated form in tridentate fashion and one half of the anionic unit containing two thiocyanate co-ligands. In complexes 2 and 3, the ligand acts in its neutral form in a tridentate manner. In complex 2, two ligand molecules coordinate the Ni(II) center, and the thiocyanate moieties remains uncoordinated. In complex 3, the Zn(II) is coordinated by one ligand molecule and two thiocyanate groups through their nitrogen atoms. Numerous hydrogen bonds consolidated the structures of complexes 1, 2, and 3 in a three-dimensional network.

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Synthesis of Functionalized 2‐Hydrazono‐3‐Thiazolines from 2‐Substituted Oxazoles through a One‐Pot Multicomponent/Rearrangement Process

Ramos,

Rossa,

Balaguez

et al. 2024

Eur J Org Chem

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The serendipitous rearrangement of an oxazole nucleus to a thiazoline ring under mild conditions is described. This transformation was achieved by a multicomponent reaction (MCR) featuring 2‐(bromomethyl)oxazoles, thiosemicarbazide, and a carbonyl compound to provide oxazole‐derived isothiosemicarbazones, which undergo oxazole ring‐opening and recyclization to 2‐hydrazono‐3‐thiazolines in a one‐pot procedure. This straightforward route produced highly functionalized thiazolines (34‐98% yield) in a chemo‐ and stereoselective manner.

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Synthesis of isothiosemicarbazones of potential antitumoral activity through a multicomponent reaction involving allylic bromides, carbonyl compounds and thiosemicarbazide

Cited by 5 publications

References 53 publications

Mechanistic Insights into the Formation of 1-Alkylidene/Arylidene-1,2,4-triazolinium Salts: A Combined NMR/Density Functional Theory Approach

Mechanistic Insights into the Formation of 1-Alkylidene/Arylidene-1,2,4-triazolinium Salts: A Combined NMR/Density Functional Theory Approach

Synthesis of Functionalized 2‐Hydrazono‐3‐Thiazolines from 2‐Substituted Oxazoles through a One‐Pot Multicomponent/Rearrangement Process

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