Facile, Single‐Step Synthesis of a Series of D‐Ring Ethisterones Substituted with 1,4‐1,2,3‐Triazoles: Preliminary Evaluation of Cytotoxic Activities

Gonzalez, Daniel Canseco; Rodríguez‐Victoria, Isaac; Apam-Ramírez, Teresa; Viviano-Posadas, Alejandro O; Serrano‐García, Juan S.; Arenaza‐Corona, Antonino; Orjuela, Adrián L.; Alí‐Torres, Jorge; Dorazco‐González, Alejandro; Morales‐Morales, David

doi:10.1002/cmdc.202200659

Cited by 2 publications

(2 citation statements)

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“…Its structural modification is of interest, given the important pharmaceutical uses of progestin . It undergoes some organic transformations typical of α-hydroxyacetylenes and has been shown to bind to transition metals, forming metal–carbon bonds . Zhou, Yin, and co-workers reported a Cu-catalyzed dehydrogenative ethisterone-phenylacetylene cross-coupling, giving 1,3-diyne .…”

Section: Resultsmentioning

confidence: 99%

Homo- and Cross-Coupling of Phenylacetylenes and α-Hydroxyacetylenes Catalyzed by a Square-Planar Rhodium Monohydride

de las Heras,

Esteruelas,

Oliván

et al. 2024

ACS Catal.

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The C–C triple bond of phenylacetylene undergoes the anti-Markovnikov addition of the Rh–H bond of RhH{κ3-P,O,P-[xant(PiPr2)2]} (1; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) to give Rh{(E)–CHCHPh}{κ3-P,O,P-[xant(PiPr2)2]} (2), which reacts with a second alkyne molecule to produce Rh(CCPh){κ3-P,O,P-[xant(PiPr2)2]} (3) and styrene before the transformation from 1 to 2 is complete. The metal center of 3 undergoes the oxidative addition of the C(sp)–H bond of another alkyne molecule to produce RhH(CCPh)2{κ3-P,O,P-[xant(PiPr2)2]} (4), which also reacts with more phenylacetylene before completing the transformation from 3 to 4. The reaction leads to Rh{(E)–CHCHPh}(CCPh)2{κ3-P,O,P-[xant(PiPr2)2]} (5), which reductively eliminates (E)-1,4-diphenyl-1-buten-3-yne to regenerate 3. Complexes 3, 4, and 5 constitute a cycle for head-to-head dimerization of phenylacetylene. Consequently, complex 1 promotes the catalytic homocoupling of terminal alkynes to (E)-enynes, including the dimerization of α-hydroxyacetylenes to (E)-enyne-diols. The rate-determining step of the couplings depends on the nature of the alkyne, being the insertion of the C–C triple bond into the Rh–H bond of a bis(acetylide)-rhodium(III)-hydride intermediate for phenylacetylenes and the reductive elimination of the product (E)-enyne-diol for α-hydroxyacetylenes. In support of the latter, complex Rh{(E)–CHCHC(OH)Ph2}{CCC(OH)Ph2}2{κ3-P,O,P-[xant(PiPr2)2]} (6) has been isolated and characterized by X-ray diffraction analysis. Complex 1 also effectively promotes the formation of compounds of the type (E)-5-phenyl-2-penten-4-yn-1-ol, by cross-coupling between phenylacetylenes and α-hydroxyacetylenes. These reactions take place through two cycles similar to the cycle that produces the homocouplings, the rate-determining step being the reductive elimination of (E)-enyn-ol for both. The catalytic performance of 1 provides good efficiency in homocoupling and cross-coupling reactions involving progestin-type compounds such as ethisterone.

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Section: Resultsmentioning

confidence: 99%

Homo- and Cross-Coupling of Phenylacetylenes and α-Hydroxyacetylenes Catalyzed by a Square-Planar Rhodium Monohydride

de las Heras,

Esteruelas,

Oliván

et al. 2024

ACS Catal.

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“…Moreover, the bonds that are formed are resistant to cleavage even by proteases. The result may be triazole systems peptide bond analogues. , Literature data show that these are 1,2,3-triazole compounds characterized by unique pharmacotherapeutic effects, especially antihypertensive, antimalarial, antioxidant, antidepressant, antimicrobial, anti-inflammatory, and anticancer effects. − The “click” method was used to obtain new steroid conjugates containing 1,2,3-triazole rings.…”

Section: Introductionmentioning

confidence: 99%

Quasi-Podands with 1,2,3-Triazole Rings from Bile Acid Derivatives: Synthesis, and Spectroscopic and Theoretical Studies

Kawka,

Koenig,

Nowak

et al. 2024

J. Org. Chem.

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An innovative approach to producing derivatives of bile acids has been devised, utilizing the principles of “click” chemistry. By employing intermolecular [3 + 2] cycloaddition between the newly developed acyl propiolic esters of bile acids and the azide groups of 1,3,5-tris(azidomethyl)benzene, a novel class of quasi-podands featuring 1,2,3-triazole rings has been synthesized. Identifying and characterizing these six compounds involved comprehensive analysis through spectral techniques (1H NMR, 13C NMR, and FT-IR), mass spectrometry, and the PM5 semiempirical method. The synthesized compounds’ pharmacotherapeutic potential has been evaluated, employing the Prediction of Activity Spectra for Substances (PASS) methodology. Additionally, molecular docking was performed for all molecules.

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Facile, Single‐Step Synthesis of a Series of D‐Ring Ethisterones Substituted with 1,4‐1,2,3‐Triazoles: Preliminary Evaluation of Cytotoxic Activities

Cited by 2 publications

References 68 publications

Homo- and Cross-Coupling of Phenylacetylenes and α-Hydroxyacetylenes Catalyzed by a Square-Planar Rhodium Monohydride

Homo- and Cross-Coupling of Phenylacetylenes and α-Hydroxyacetylenes Catalyzed by a Square-Planar Rhodium Monohydride

Quasi-Podands with 1,2,3-Triazole Rings from Bile Acid Derivatives: Synthesis, and Spectroscopic and Theoretical Studies

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