Intercepting the Banert cascade with nucleophilic fluorine: direct access to α-fluorinated <i>N</i>H-1,2,3-triazoles

Alexander, Juliana R.; Kevorkian, Paul V.; Topczewski, Joseph J.

doi:10.1039/d1cc01179k

Cited by 6 publications

(3 citation statements)

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“…This viewpoint inspires a new molecular design approach for PSs using small organic thermally activated delayed fluorescence (TADF) emitters that are designed to have an ultrasmall Δ E ST (0.01–0.05 eV). 10–14 However, due to their non-biocompatibility, TADF emitters have not been widely used in biomedical applications. 15–17 Thiocarbonyl substitution at the carbonyl group of conventional fluorophores is another reported PS design strategy, which can dramatically enhance their abilities to generate ROS.…”

Section: Introductionmentioning

confidence: 99%

Thermally activated delayed fluorescence emitters: a thionation approach toward next-generation photosensitizers

et al. 2023

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Section: Introductionmentioning

confidence: 99%

Thermally activated delayed fluorescence emitters: a thionation approach toward next-generation photosensitizers

et al. 2023

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“…18 The Banert cascade is an efficient synthetic strategy to prepare 1H-1,2,3-triazoles from propargylic azides (Scheme 1b). [19][20][21][22][23][24][25][26][27] Klaus Banert reported the first synthesis of substituted 1H-1,2,3-triazole via [3,3]-sigmatropic rearrangement in 1989. 19 Then, Loren and Sharpless, following the tradition of affiliating important reactions with their discoverers, called to this reaction route the Banert cascade.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Fate of the Banert Cascade of Propargylic Azides. Sigmatropic versus Prototropic Pathway

Villareal-Parra

Gresia

Labadié

et al. 2023

Preprint

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The Banert cascade is an efficient synthetic strategy for obtaining 4,5-disubstituted 1,2,3-triazoles. The reaction can proceed via a sigmatropic or prototropic mechanism depending on the substrate and the conditions. In this work, the mechanism of both pathways from propargylic azides with different electronic features were investigated using DFT, QTAIM and NBO approaches. The calculated energies barriers were consistent with the experimental data. Three patterns of electron density distribution on the transition structures were observed, which reflected the behaviours of the reactants in the Banert cascade. The stronger conjugative effects were associated with lower/higher free activation energies of sigmatropic/prototropic reactions, respectively. A clear relationship between the accumulation of the charge at the C3 atom of propargylic azides with the energy barriers for prototropic reactions was found. Thus, the obtained results would allow the prediction of the reactions course evaluating reactants.

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“…The Banert cascade is an efficient synthetic strategy to prepare 1 H -1,2,3-triazoles from propargylic azides (Scheme b). − Klaus Banert reported the first synthesis of substituted 1 H -1,2,3-triazole via a [3,3]-sigmatropic rearrangement in 1989 . Then, Loren and Sharpless, following the tradition of affiliating important reactions with their discoverers, named this reaction route the Banert cascade .…”

Section: Introductionmentioning

confidence: 99%

Understanding the Fate of the Banert Cascade of Propargylic Azides: Sigmatropic versus Prototropic Pathway

Villarreal-Parra,

Di Gresia,

Labadie

et al. 2023

J. Org. Chem.

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The Banert cascade is an efficient synthetic strategy for obtaining 4,5-disubstituted 1,2,3-triazoles. The reaction can proceed via a sigmatropic or prototropic mechanism depending on the substrate and the conditions. In this work, the mechanisms of both pathways from propargylic azides with different electronic features were investigated using density functional theory, quantum theory of atoms in molecules, and natural bond orbital approaches. The calculated energy barriers were consistent with the experimental data. Three patterns of electron density distribution on the transition structures were observed, which reflected the behaviors of the reactants in the Banert cascade. The stronger conjugative effects were associated with lower/higher free activation energies of sigmatropic/prototropic reactions, respectively. A clear relationship between the accumulation of the charge at the C3 atom of propargylic azides with the energy barriers for prototropic reactions was found. Thus, the obtained results would allow the prediction of the reaction’s course by evaluating reactants.

show abstract

Intercepting the Banert cascade with nucleophilic fluorine: direct access to α-fluorinated NH-1,2,3-triazoles

Abstract: The Banert Cascade of propargylic azides is a unique pathway to access α-functionalized NH-1,2,3-triazoles. The resulting het-erocycles have documented utility as unique bioisosteres. Previously, the scope of the nucleophile used...

Cited by 6 publications

References 61 publications

Thermally activated delayed fluorescence emitters: a thionation approach toward next-generation photosensitizers

Thermally activated delayed fluorescence emitters: a thionation approach toward next-generation photosensitizers

Understanding the Fate of the Banert Cascade of Propargylic Azides. Sigmatropic versus Prototropic Pathway

Understanding the Fate of the Banert Cascade of Propargylic Azides: Sigmatropic versus Prototropic Pathway

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