Fluorine Containing Diazines. Synthesis and Properties

“…In the pursuit of other potential fluorinated scaffolds with unique chemical properties, diazaperfluoro-heteroaromatics such as perfluoropyrazine (1), perfluoropyrimidine (2), and perfluoropyridazine (3) are immediately attractive targets for chemical modeling (Figure 1) [18][19][20][21]. These molecules have been of increasing significance in the literature over the last several decades [22].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Prediction and Explanation of Reaction Site Selectivity in the Addition of a Phenoxy Group to Perfluoropyrimidine, Perfluoropyridazine, and Perfluoropyrazine

et al. 2021

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Perfluoroaromatics, such as perfluoropyridine and perfluorobenzene, are privileged synthetic scaffolds in organofluorine methodology, undergoing a series of regioselective substitution reactions with a variety of nucleophiles. This unique chemical behavior allows for the synthesis of many perfluoroaromatic derived molecules with unique and diverse architectures. Recently, it has been demonstrated that perfluoropyridine and perfluorobenzene can be utilized as precursors for a variety of materials, ranging from high performance polyaryl ethers to promising drug scaffolds. In this work, using density functional theory, we investigate the possibility of perfluoropyrimidine, perfluoropyridazine, and perfluoropyrazine participating in similar substitution reactions. We have found that the first nucleophilic addition of a phenoxide group substitution on perfluoropyrimidine and on perfluoropyridazine would happen at a site para to one of the nitrogen atoms. While previous literature points to mesomeric effects as the primary cause of this phenomenon, our work demonstrates that this effect is enhanced by the fact that the transition states for these reactions result in bond angles that allow the phenoxide to π-complex with the electron-deficient diazine ring. The second substitution on perfluoropyrimidine and on perfluoropyridazine is most likely to happen at the site para to the other nitrogen. The second substitution on perfluoropyrazine is most likely to happen at the site para to the first substitution. The activation energies for these reactions are in line with those reported for perfluoropyridine and suggest that these platforms may also be worth investigation in the lab as possible monomers for high performance polymers.

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“…7 With significant developments in Suzuki, Chan− Lam, photoredox, and other coupling reactions, cyclopropanederived boronic acids, boronates, and trifluoroborates became essential tools to introduce cyclopropyl fragments into (hetero)aromatic molecules through the C−C and C− heteroatom bond formation. 2 Among the known methods for the preparation of boronic derivatives, decarboxylative borylation (or borodecarboxylation) 8−10 is especially promising since it commences from carboxylic acids that historically have been one of the most widely used and readily accessible building block categories. 11 The known approaches to the decarboxylative borylation of carboxylic acids involve their transformation into the so-called redox-active esters (e.g., N-hydroxyphthalimide (NHPI) derivatives) and further borylation thereof with a diboron compound, e.g., B 2 Pin 2 (Pin-pinacol residue) (Scheme 1, A).…”

mentioning

confidence: 99%

Organocatalytic Decarboxylative Borylation of Cyclopropane N-Hydroxyphthalimide Esters

Krokhmaliuk,

Kleban,

Rassukana

et al. 2024

J. Org. Chem.

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A convenient protocol for the two-step organocatalytic decarboxylative borylation of 1,1-disubstituted, 1,2-disubstituted, and bicyclic cyclopropane carboxylic acids via the corresponding Nhydroxyphthalimide esters is described, using tert-butyl or ethyl isonicotinate as an inexpensive and readily available catalyst. The scope of the method was demonstrated, being limited mainly by electron-poor substrates. The reaction sequence showed good scalability (up to 51.5 g) and excellent trans diastereoselectivity (for the case of 1,2-disubstituted substrates). Therefore, the proposed approach is a very promising alternative to other existing (i.e., metal-catalyzed) methods for borodecarboxylation.

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Fluorine Containing Diazines. Synthesis and Properties

Cited by 7 publications

References 599 publications

Review on fluorinated nucleoside/non-nucleoside FDA-approved antiviral drugs

Review on fluorinated nucleoside/non-nucleoside FDA-approved antiviral drugs

Theoretical Prediction and Explanation of Reaction Site Selectivity in the Addition of a Phenoxy Group to Perfluoropyrimidine, Perfluoropyridazine, and Perfluoropyrazine

Organocatalytic Decarboxylative Borylation of Cyclopropane N-Hydroxyphthalimide Esters

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