Structure and Properties of Nitrogen-Rich 1,4-Dicyanotetrazine, C<sub>4</sub>N<sub>6</sub>: A Comparative Study with Related Tetracyano Electron Acceptors

Vo, Hoa Lan; Arthur, Jordan L.; Capdevila‐Cortada, Marçal; Lapidus, Saul H.; Stephens, Peter W.; Novoa, Juan J.; Arif, Atta M.; Nagi, Ramneet K.; Bartl, Michael H.; Miller, Joel S.

doi:10.1021/jo5014004

Cited by 5 publications

(4 citation statements)

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“…These substrate scopes indicate that our dealkenylative C(sp 3 )–C(sp 2 ) coupling protocol is compatible with myriad functionalities including alcohol, phenol, alkene, alkyne, epoxide, ketone, aldehyde, enone, cyanide, ester, heterocycles, pentafluorobenzene, amide, tosylate, and boronic ester, furnishing the products in synthetically useful yields. We noted that unprotected amines were not tolerated during the intermolecular DA reaction of alkene with 6 , but the aniline was tolerated to some extent, furnishing the corresponding coupling product in a low yield ( 8t ).…”

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confidence: 87%

Dealkenylative Ni-Catalyzed Cross-Coupling Enabled by Tetrazine and Photoexcitation

et al. 2021

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A new and general method to functionalize the C(sp 3 )−C(sp 2 ) bond of alkyl and alkene linkages has been developed, leading to the dealkenylative generation of carbon-centered radicals that can be intercepted to undergo Ni-catalyzed C(sp 3 )−C(sp 2 ) cross-coupling. This one-pot protocol leverages the easily procured alkene feedstocks for organic synthesis with excellent functional group compatibility without the need for a photoredox catalyst.

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confidence: 87%

Dealkenylative Ni-Catalyzed Cross-Coupling Enabled by Tetrazine and Photoexcitation

et al. 2021

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“…In the first part of the study, we focused on the inverse electrondemand Diels-Alder cycloaddition reactions of dibenzosuberenone (1) with s-tetrazines 2a-l ( Figure 2), which were synthesized according to the literature procedures (2j was synthesized by acetylation of 2i, while 2b and 2g were purchased) [57][58][59][60][61][62][63].…”

Section: Synthesismentioning

confidence: 99%

Synthesis of dibenzosuberenone-based novel polycyclic π-conjugated dihydropyridazines, pyridazines and pyrroles

Koçak¹,

Daştan²

2021

Beilstein J. Org. Chem.

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The synthesis of novel polycyclic π-conjugated dihydropyridazines, pyridazines, and pyrroles was studied. Dihydropyridazine dyes were synthesized by inverse electron-demand Diels–Alder cycloaddition reactions between a dibenzosuberenone and tetrazines that bear various substituents. The pyridazines were synthesized in high yields by oxidation of dihydropyridazine-appended dibenzosuberenones with PIFA or NO. p-Quinone derivatives of pyridazines were also obtained by H-shift isomerization following the inverse electron-demand Diels–Alder reaction of tetrazines with p-quinone dibenzosuberenone. Then these pyridazines were converted to the corresponding pyrroles by reductive treatment with zinc. It was observed that all the dihydropyridazines obtained gave absorbance and emission at long wavelengths.

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“…The structure of the simple 3,6-bis(1-Aziridinyl)-1,2,4,5-tetrazine, FIZJIH (Figure 34) [167], and 1,2,4,5tetrazine-3,6-dicarbonitrile, JOYXEC (Figure 35) [168], provide some valuable examples. The peculiarity of these structures is that they both contain very simple organic molecules constituted by the tetrazine core and decorated with N-containing pendants, thus are not expected to exhibit any peculiar supramolecular interaction beyond simple π-π stacking forces.…”

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confidence: 99%

Anion-π and lone pair-π interactions with s-tetrazine-based ligands

Savastano

García-Gallarín

Torre

et al. 2019

Coordination Chemistry Reviews

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Most of traditional and contemporary interest in s-tetrazine derivatives focuses onto their redox properties, reactivity and energy density. In recent times, however, an increasing number of reports highlighted the possible usefulness of the s-tetrazine moiety as a binding site for anionic and electron rich species, according to the high and positive quadrupolar moment of this heterocycle and the consequent strength of anion-π and lone pair-π interactions. Herein, after giving a quick perspective on s-tetrazine properties and on how they foster these types of π interactions, we present statistical and critical examination of the available structural data, doing justice to the debated topic of the existence and directionality of anion-and lone pair-π interactions. Finally, available literature material concerning the usage of s-tetrazine as supramolecular binding site in solution, i.e. paving the way to applications such as molecular recognition and sensing, is presented and discussed. Contents 1. Introduction 2. s-Tetrazine Synthesis & Properties 2.1. Synthesis of s-tetrazine derivatives 2.2. General perspective on the properties and applications s-tetrazines 2.3. Anion-π and lone pair-π: nature of the interactions and relevance of the s-tetrazine ring 3. Anion-π and lone pair-π interactions with s-tetrazines in the solid-state: CSD Survey 3.1. Methodology and rationale of the survey 3.2. Structural data analysis 4. Selected evidences of anion-π and lone pair-π interactions with s-tetrazines in the solid state 5. Anion-π and lone pair-π interactions with s-tetrazines in solution 6. Conclusions Appendix A. Supplementary data Referencesthe aromatic s-tetrazine ring enables compact molecular packings which are essential to realize substances with a high (volumetric) energy density [116,117]. This is a field that continues very active in seeking for new s-tetrazine derivatives of interest [118][119][120].Other important applications of s-tetrazines derive from their particular reactivity, that serves as the base of the usefulness that these structures are proving in molecular biology studies, as reacting partners in bioorthogonal chemistry [121] methods (a field that has boosted the research and literature devoted to stetrazines from the first 2000s) [84,122]. These applications take advantage of two properties of stetrazines: i) the propensity of the s-tetrazine nucleus to act as 2,3-diazadiene in fast inverse-electrondemand Diels-Alder (iedDA) reactions with alkenes and alkynes that affords, in a first term, a bicyclic adduct which immediately suffers a retro-Diels-Alder (rDA) reaction, evolving N 2 , to give rise to dihydropyridazines or aromatic pyridazines, respectively (Scheme 2) [123,124]; ii) the inertness of s-tetrazine derivatives towards natural substances under biological conditions. Scheme 2 to be inserted about here.But the property that focused our interest in s-tetrazines, and constitutes the main subject of this review, is their ability to establish non-covalent bonds to negatively charged species (a...

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Structure and Properties of Nitrogen-Rich 1,4-Dicyanotetrazine, C₄N₆: A Comparative Study with Related Tetracyano Electron Acceptors

Cited by 5 publications

References 77 publications

Dealkenylative Ni-Catalyzed Cross-Coupling Enabled by Tetrazine and Photoexcitation

Dealkenylative Ni-Catalyzed Cross-Coupling Enabled by Tetrazine and Photoexcitation

Synthesis of dibenzosuberenone-based novel polycyclic π-conjugated dihydropyridazines, pyridazines and pyrroles

Anion-π and lone pair-π interactions with s-tetrazine-based ligands

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Structure and Properties of Nitrogen-Rich 1,4-Dicyanotetrazine, C4N6: A Comparative Study with Related Tetracyano Electron Acceptors

Cited by 5 publications

References 77 publications

Dealkenylative Ni-Catalyzed Cross-Coupling Enabled by Tetrazine and Photoexcitation

Dealkenylative Ni-Catalyzed Cross-Coupling Enabled by Tetrazine and Photoexcitation

Synthesis of dibenzosuberenone-based novel polycyclic π-conjugated dihydropyridazines, pyridazines and pyrroles

Anion-π and lone pair-π interactions with s-tetrazine-based ligands

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Structure and Properties of Nitrogen-Rich 1,4-Dicyanotetrazine, C₄N₆: A Comparative Study with Related Tetracyano Electron Acceptors