Regio- and stereoselective synthesis of nitrofunctionalized 1,2-oxazolidine analogs of nicotine

Fryźlewicz, Agnieszka; Łapczuk-Krygier, Agnieszka; Kula, Karolina; Demchuk, Oleg M.; Dresler, Ewa; Jasiński, Radomir

doi:10.1007/s10593-020-02631-6

Cited by 19 publications

(12 citation statements)

References 22 publications

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“…It was found that the isolated compound (3a or 4a) gave a pseudo-molecular ion 320,9601mDa [M-H] − (see Supplementary Materials) which corresponds with the proposed C 11 H 8 N 2 O 3 Cl 3 molecular formula. Bands typical for the NO 2 group [35], -N-O- [11,36], and -C=N- [11] moieties in the heterocyclic ring as well as C-Cl bond [35] vibrations were detected in its IR spectrum. Information about stereochemistry of the isolated compound was provided by 1 H NMR spectroscopy.…”

Section: Experimental Studymentioning

confidence: 99%

The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study

et al. 2021

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The regioselective zw-type [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile N-oxides (NOs) with trichloronitropropene (TNP) have been both experimentally and theoretically studied within the Molecular Electron Density Theory (MEDT). Zwitterionic NOs behave as moderate nucleophiles while TNP acts as a very strong electrophile in these polar 32CA reactions of forward electron density flux, which present moderate activation Gibbs free energies of 22.8–25.6 kcal·mol−1 and an exergonic character of 28.4 kcal·mol−1 that makes them irreversible and kinetically controlled. The most favorable reaction is that involving the most nucleophilic MeO-substituted NO. Despite Parr functions correctly predicting the experimental regioselectivity with the most favorable O-CCCl3 interaction, these reactions follow a two-stage one-step mechanism in which formation of the O-C(CCl3) bond takes place once the C-C(NO2) bond is already formed. The present MEDT concludes that the reactivity differences in the series of NOs come from their different nucleophilic activation and polar character of the reactions, rather than any mechanistic feature.

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Section: Experimental Studymentioning

confidence: 99%

The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study

et al. 2021

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“…So, TMH substituted conjugated nitroalkenes attract the attention of various research centers. In particular, 3,3,3-trichloro-1-nitroprop-1-ene was recently intensively tested as a component of different type cycloadditions involving diazocompounds [ 8 , 9 ], nitrile N -oxides [ 10 ], and especially nitrones [ 11 , 12 , 13 , 14 ]. Regarding 3,3,3-trifluor-1-nitroprop-1-ene, many interesting scientific works are also available at the present time [ 4 , 5 , 6 , 15 , 16 ].…”

Section: Introductionmentioning

confidence: 99%

The First Examples of [3+2] Cycloadditions with the Participation of (E)-3,3,3-Tribromo-1-Nitroprop-1-Ene

et al. 2022

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The first examples of [3+2] cycloaddition reactions between 3,3,3-tribromo-1-nitroprop-1-ene (TBMN) were explored on the basis of experimental and theoretical approaches. It was found that reactions involving TBMN and diarylnitrones realized with full regio- and stereoselectivity lead to respective 3,4-cis-4,5-trans-4-nitroisoxazolidines. The regioselecticity and the molecular mechanism of title processes was analyzed on the basis of the advanced DFT computational study.

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“…Recently, experimental and theoretical determinations of activation enthalpies and kinetic isotope effects (directly correlated with the degree of rehybridization, and thus the degree of advancement of new bonds) for different types of cycloaddition reactions have been performed. In these works, a perfect agreement was obtained between the experimentally measured parameters and those calculated with the use of the B3LYP functional [ 47 , 48 , 49 ]. Subsequently, for the model reaction, analogous calculations were performed using more advanced levels of theory.…”

Section: Computational Proceduresmentioning

confidence: 96%

On the Question of Zwitterionic Intermediates in the [3 + 2] Cycloaddition Reactions between C-arylnitrones and Perfluoro 2-Methylpent-2-ene

et al. 2021

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The molecular mechanism of the [3 + 2] cycloaddition reaction between C-arylnitrones and perfluoro 2-methylpent-2-ene was explored on the basis of DFT calculations. It was found that despite the polar nature of the intermolecular interactions, as well as the presence of fluorine atoms near the reaction centers, all reactions considered cycloaddition proceed via a one-step mechanism. All attempts for the localization of zwitterionic intermediates on the reaction paths were not successful. Similar results were obtained regardless of the level of theory applied.

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Regio- and stereoselective synthesis of nitrofunctionalized 1,2-oxazolidine analogs of nicotine

Cited by 19 publications

References 22 publications

The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study

The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study

The First Examples of [3+2] Cycloadditions with the Participation of (E)-3,3,3-Tribromo-1-Nitroprop-1-Ene

On the Question of Zwitterionic Intermediates in the [3 + 2] Cycloaddition Reactions between C-arylnitrones and Perfluoro 2-Methylpent-2-ene

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