3,5-Dioxopimelates as new synthetic building blocks. Cyclocondensation with 1,2-, 1,3- and 1,4-dinucleophiles

Bendrath, Franziska; Specowius, Verena; Michalik, Dirk; Langer, Peter

doi:10.1016/j.tet.2012.05.119

Cited by 8 publications

(10 citation statements)

References 46 publications

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“…The dimethyl benzodiazepine(diylidene)diacetates 1a and 1b were synthesized by the procedure described in Bendrath et al [2] 1 H NMR spectra (300.13 and 500.13 MHz) and 13 C NMR spectra (75.5 and 125.8 MHz) of 1a and 1b were recorded on Bruker spectrometers AVANCE 300 and AVANCE 500 in CDCl 3 , (D 6 )DMSO and (D 7 )DMF solution (concentration ≈ 0.1 M) at different temperatures (the sample temperature was measured by means of thermometer liquids [12] ). [1,4] diazepine-2,4(3H)-diylidene) (2Z,2 0 Z)diacetate): 1 H NMR (500.13 MHz, CDCl 3 , 298 K): δ = 10.37 (s, 2H, NH); 7.14 (s, 2H, H-9(12)); 4.79 (s, 2H, H-2(6)); 3.70 (s, 6H, OMe); 2.96 (s, 2H, H-4).…”

Section: Methodsmentioning

confidence: 99%

“…[1] In a previous paper, we reported the synthesis of a series of dimethyl benzodiazepine(diylidene)diacetates 1 by cyclization reaction of 3,5-dioxopimelates with 1,2-diaminobenzenes (Scheme 1). [2] Compounds 1 appeared in CDCl 3 solution as one species, which is stabilized by two intramolecular hydrogen bonds. In the 1 H and 13 C nuclear magnetic resonance (NMR) spectra, some resonance signals appeared as broadened or doubled, which suggested a dynamic process.…”

Section: Introductionmentioning

confidence: 99%

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NMR spectroscopic and theoretical study on the isomerism of dimethyl benzodiazepine(diylidene)diacetates

Michalik

Jiao

Langer

2022

Magnetic Reson in Chemistry

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The isomerism of dimethyl 2,2′‐(7,8‐dichloro‐1H‐benzo[b][1,4]diazepine‐2,4‐(3H,5H)diylidene)diacetate (1a) and dimethyl 2,2′‐(7,8‐dichloro‐3‐methyl‐1H‐benzo[b][1,4]diazepine‐2,4‐(3H,5H)diylidene)diacetate (1b) was investigated by 1H, 13C and 15N nuclear magnetic resonance (NMR) spectroscopy. In CDCl3 solution, inversion of the diazepine ring was observed, whereas in (D6)DMSO and (D7)DMF solution, besides the ring inversion, a partial cleavage of one chelate ring appeared connected with (E/Z) isomerization about one of the exocyclic C=C bonds. Gibbs free energies (ΔG) and free activation energies (ΔG≠) were calculated based on B3PW91‐SCRF/ZVP DFT computations. Agreement between NMR data and density functional theory (DFT) computations was found.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

NMR spectroscopic and theoretical study on the isomerism of dimethyl benzodiazepine(diylidene)diacetates

Michalik

Jiao

Langer

2022

Magnetic Reson in Chemistry

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“…The cyclization of 3,5-dioxopimelates 25a,b with various hydrazines afforded hydrazones 51a-g in moderate to excellent yields (Scheme 27). 31 The cyclizations proceeded via the two keto groups of 25a,b which are more electrophilic than the ester groups. The cyclization of 3,5-dioxopimelate 25a with urea and thioureas afforded pyrimidinone 52a and pyrimidinethione 52b in excellent yields, respectively (Scheme 28).…”

Section: Cyclizationsmentioning

confidence: 99%

“…The cyclization of 3,5-dioxopimelate 25a with urea and thioureas afforded pyrimidinone 52a and pyrimidinethione 52b in excellent yields, respectively (Scheme 28). 31 The cyclizations proceeded regioselectively via the nitrogen atoms. The products show a dynamic nature in NMR (tautomerism).…”

Section: Cyclizationsmentioning

confidence: 99%

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Synthesis and Reactions of 1,3,5-Tri- and 1,3,5,7-Tetracarbonyl Compounds

Langer

2021

Synlett

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The reaction of 1,3-bis(silyloxy)-1,3-butadienes with functionalized and nonfunctionalized acid chlorides and bis(acid chlorides) gives rise to the formation of a great variety of 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds and cyclic products derived from them. Examples include functionalized and nonfunctionalized 3,5-dioxopentanoates, 3,5-dioxopimelates, 3-alkylidene-3H-isobenzofuran-1-ones, salicylates, 3(2H)furanones, and 3-oxo-4-sulfonylesters. Methylation and cyclopropanation reactions of 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds do not provide access to the expected permethylated and cyclopropanated polycarbonyl compounds. However, the latter could be prepared by stepwise protocols. The reaction of 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds with dinucleophiles resulted in cyclization reactions to give a variety of heterocyclic structures.1 Introduction2 Reactions of 1,3-Bis(silyloxy)-1,3-butadienes with Acid Chlorides3 Reactions of 1,3,5-Tri- and 1,3,5,7-Tetracarbonyl Compounds4 Conclusion

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Funktionalisierung von Chlorotonilen: Dehalogenil als vielversprechende Leitverbindung für die in vivo‐Anwendung

Hofer,

Deschner,

Jézéquel

et al. 2024

Angewandte Chemie

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The natural product chlorotonil displays high potency against multidrug‐resistant Gram‐positive bacteria and Plasmodium falciparum. Yet, its scaffold is characterized by low solubility and oral bioavailability but progress was recently made to enhance these properties. Applying late‐stage functionalization, we aimed to further optimize the molecule. Previously unknown reactions including a sulfur‐mediated dehalogenation were revealed. Dehalogenil, the product of this reaction, was identified as the most promising compound so far, as this new derivative displayed improved solubility and in vivo efficacy while retaining excellent antimicrobial activity. We confirmed superb activity against multidrug‐resistant clinical isolates of Staphylococcus aureus and Enterococcus spp. and mature transmission stages of Plasmodium falciparum. We also demonstrated favorable in vivo toxicity, pharmacokinetics and efficacy in infection models with S. aureus. Taken together, these results identify dehalogenil as an advanced lead molecule.

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3,5-Dioxopimelates as new synthetic building blocks. Cyclocondensation with 1,2-, 1,3- and 1,4-dinucleophiles

Cited by 8 publications

References 46 publications

NMR spectroscopic and theoretical study on the isomerism of dimethyl benzodiazepine(diylidene)diacetates

NMR spectroscopic and theoretical study on the isomerism of dimethyl benzodiazepine(diylidene)diacetates

Synthesis and Reactions of 1,3,5-Tri- and 1,3,5,7-Tetracarbonyl Compounds

Funktionalisierung von Chlorotonilen: Dehalogenil als vielversprechende Leitverbindung für die in vivo‐Anwendung

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