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Mechanistic DFT Study of 1,3-Dipolar Cycloadditions of Azides with Guanidine

Antol, Ivana; Glasovac, Zoran; Margetić, Davor (2023) Mechanistic DFT Study of 1,3-Dipolar Cycloadditions of Azides with Guanidine. Molecules, 28 (5). ISSN 1420-3049

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Density functional calculations SMD(chloroform)//B3LYP/6-311+G(2d, p) were employed in the computational study of 1, 3-dipolar cycloadditions of azides with guanidine. The formation of two regioisomeric tetrazoles and their rearrangement to cyclic aziridines and open- chain guanidine products were modeled. The results suggest the feasibility of an uncatalyzed reaction under very drastic conditions since the thermodynamically preferred reaction path (a), which involves cycloaddition by binding the carbon atom from guanidine to the terminal azide nitrogen atom, and the guanidine imino nitrogen with the inner N atom from the azide, has an energy barrier higher than 50 kcal mol−1. The formation of the other regioisomeric tetrazole (imino nitrogen interacts with terminal N atom of azide) in direction (b) can be more favorable and proceed under milder conditions if alternative activation of the nitrogen molecule releases (e.g., photochemical activation), or deamination could be achieved because these processes have the highest barrier in the less favorable (b) branch of the mechanism. The introduction of substituents should favorably affect the cycloaddition reactivity of the azides, with the greatest effects expected for the benzyl and perfluorophenyl groups.

Item Type: Article
Uncontrolled Keywords: 1, 3-dipolar cycloadditions ; DFT calculations ; azides ; guanidines ; tetrazoles
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Division of Organic Chemistry and Biochemistry
Project titleProject leaderProject codeProject type
Cikloadicijske strategije prema policikličkim gvanidinimaMargetić, DavorIP-2018-01-3298HRZZ
Depositing User: Ivana Antol
Date Deposited: 12 Apr 2023 13:06
DOI: 10.3390/molecules28052342

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