Iron‐ or Zinc‐Mediated Synthetic Approach to Enantiopure Dihydroquinoxalinones

Li, Dazhi; Ollevier, Thierry

doi:10.1002/ejoc.201801639

Cited by 13 publications

(7 citation statements)

References 60 publications

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“…The polyamines derivatives were obtained in reactions with FNBT, CNBF, and BPI, as reported (Figure 1) [14][15][16]. CNBF and FNBT readily undergo a nucleophilic aromatic substitution; hence, numerous publications describe the usage of these reagents to synthesize heterocyclic compounds for medical applications [32,33] and were also applied for the determination of biogenic amines. However, to the best of our knowledge, there is a lack of information on spermidine and spermine derivatives' structures.…”

Section: Structural Characteristics Of the Obtained Derivativesmentioning

confidence: 99%

The Selection of the Best Derivatization Reagents for the Determination of Polyamines in Home-Made Wine Samples

et al. 2023

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The procedures of putrescine, spermine, spermidine, and cadaverine derivatization using 2-chloro-1,3-dinitro-5-(trifluoromethyl)benzene, 1-fluoro-2-nitro-4-(trifluoromethyl) benzene, and 3,5-bis-(trifluoromethyl)phenyl isothiocyanate for chromatographic determination in home-made wine samples are compared in the present study. The procedures discussed were compared regarding simplicity, linearity, precision, and accuracy. The polyamines derivatives were isolated and characterized by X-ray crystallography and 1H, 13C, and 19F NMR spectroscopy. The obtained structures of aliphatic amines showed that all amino groups, four in spermine, two in putrescine and cadaverine, and three in spermidine, regardless of the applied reagent, were substituted. The applicability of the described procedures was tested during the chromatographic analysis of the compounds’ content in home-made wines. For this purpose, a simple and environmentally friendly sample preparation procedure was developed. The obtained results present the derivatization of polyamines with 1-fluoro-2-nitro-4-(trifluoromethyl)benzene as a better choice for the determination of these compounds in food samples.

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Section: Structural Characteristics Of the Obtained Derivativesmentioning

confidence: 99%

The Selection of the Best Derivatization Reagents for the Determination of Polyamines in Home-Made Wine Samples

et al. 2023

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“…Dihydroquinoxalinones are bioactive compounds of high interest, due to their anticancer [ 42 , 43 , 44 ] and anti-inflammatory [ 45 ] properties, as well as their activity against neurological diseases [ 46 ] ( Scheme 2 ). Dihydroquinaxolinone derivatives have been mainly synthesized via coupling of o -nitroaryl- or o -aminoaryl halides with amino acids [ 43 , 45 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 ], or transition metal-catalyzed asymmetric hydrogenation of the corresponding quinoxaline derivatives ( Scheme 2 ) [ 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 ]. However, these methods required air-sensitive catalysts, toxic organic solvents, and several ligands.…”

Section: Introductionmentioning

confidence: 99%

Supported Gold Nanoparticle-Catalyzed Selective Reduction of Multifunctional, Aromatic Nitro Precursors into Amines and Synthesis of 3,4-Dihydroquinoxalin-2-Ones

et al. 2022

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The synthesis of 3,4-dihydroquinoxalin-2-ones via the selective reduction of aromatic, multifunctional nitro precursors catalyzed by supported gold nanoparticles is reported. The reaction proceeds through the in situ formation of the corresponding amines under heterogeneous transfer hydrogenation of the initial nitro compounds catalyzed by the commercially available Au/TiO2-Et3SiH catalytic system, followed by an intramolecular C-N transamidation upon treatment with silica acting as a mild acid. Under the present conditions, the Au/TiO2-TMDS system was also found to catalyze efficiently the present selective reduction process. Both transfer hydrogenation processes showed very good functional-group tolerance and were successfully applied to access more structurally demanding products bearing other reducible moieties such as chloro, aldehyde or methyl ketone. An easily scalable (up to 1 mmol), low catalyst loading (0.6 mol%) synthetic protocol was realized, providing access to this important scaffold. Under these mild catalytic conditions, the desired products were isolated in good to high yields and with a TON of 130. A library analysis was also performed to demonstrate the usefulness of our synthetic strategy and the physicochemical profile of the derivatives.

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“…[13] Both approaches, although based on cheap chiral sources, somewhat suffered of substrate‐dependent applicability or partial racemization. [14] More recently, Ir‐ and Pd‐catalysed hydrogenation of quinoxalinones enabled to achieve consistently high level of asymmetric induction (Scheme 1 c,i ). [15] The process was also successfully expanded, employing chiral phosphoric acids/Hantzsch ester systems (Scheme 1 c,i i).…”

Section: Introductionmentioning

confidence: 99%

Catalytic Enantioselective Access to Dihydroquinoxalinones via Formal α‐Halo Acyl Halide Synthon in One Pot

et al. 2021

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An enantioselective one‐pot catalytic strategy to dihydroquinoxalinones, featuring novel 1‐phenylsulfonyl‐1‐cyano enantioenriched epoxides as masked α‐halo acyl halide synthons, followed by a domino ring‐opening cyclization (DROC), is documented. A popular quinine‐derived urea served as the catalyst in two out of the three steps performed in the same solvent using commercially available aldehydes, (phenylsulfonyl)acetonitrile, cumyl hydroperoxide and 1,2‐phenylendiamines. Medicinally relevant 3‐aryl/alkyl‐substituted heterocycles are isolated in generally good to high overall yield and high enantioselectivity (up to 99 % ee). A rare example of excellent reusability of an organocatalyst at higher scale, subjected to oxidative conditions, is demonstrated. Mechanistically, labile α‐ketosulfone has been detected as the intermediate involved in the DROC process. Theoretical calculations on the key epoxidation step rationalize the observed stereocontrol, highlighting the important role played by the sulfone group.

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Iron‐ or Zinc‐Mediated Synthetic Approach to Enantiopure Dihydroquinoxalinones

Cited by 13 publications

References 60 publications

The Selection of the Best Derivatization Reagents for the Determination of Polyamines in Home-Made Wine Samples

The Selection of the Best Derivatization Reagents for the Determination of Polyamines in Home-Made Wine Samples

Supported Gold Nanoparticle-Catalyzed Selective Reduction of Multifunctional, Aromatic Nitro Precursors into Amines and Synthesis of 3,4-Dihydroquinoxalin-2-Ones

Catalytic Enantioselective Access to Dihydroquinoxalinones via Formal α‐Halo Acyl Halide Synthon in One Pot

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