Ring-fused hexahydro-1,2,4,5-tetrazines: synthesis, structure, and mechanistic studies on isolable rotational isomers

Toda, Yasunori; Kooguchi, Airi; Sukegawa, Kimiya; Kikuchi, Ayaka; Suga, Hiroyuki

doi:10.1039/d2cc06170h

Chem. Commun.

2023

DOI: 10.1039/d2cc06170h

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Ring-fused hexahydro-1,2,4,5-tetrazines: synthesis, structure, and mechanistic studies on isolable rotational isomers

Yasunori Toda

Airi Kooguchi

Kimiya Sukegawa

et al.

Abstract: We designed conformationally stable rotational isomers around the C(sp2)-C(sp3) axis at the C3-position of hexahydro-1,2,4,5-tetrazines. Isolation of each rotamer by silica gel column chromatography was successfully achieved at room temperature....

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2024

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Conformation Analysis and Stereodynamics of Symmetrically ortho-Disubstituted Carvacrol Derivatives

Đorđević Zlatković,

Radulović,

Dangalov

et al. 2024

Molecules

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The design and synthesis of analogs of natural products can be a valuable source of medicinal preparations for the pharmaceutical industry. In the present study, the structural elucidation of eleven derivatives of 2,4-dihalogeno substituted synthetic analogues of the natural compound carvacrol was carried out by means of NMR experiments, and of another thirteen by DFT calculations. By selective NOE experiments and the irradiation of CH signals of the isopropyl group, individual conformers were assigned as syn and anti. By comparing GIAO/B3LYP/6-311++G(d,p)-calculated and experimentally measured vicinal 3JCH spin-spin constants, this assignment was confirmed. An unusual relationship is reported for proton-carbon vicinal couplings: 3JCH (180°) < 3JCH (0°). The conformational mobility of carvacrols was studied by 2D EXSY spectra. The application of homonuclear decoupling technique (HOBS) to these spectra simplifies the spectra, improves resolution without reducing the sensitivity, and allows a systematic examination of the rotational barrier of all compounds via their CH signals of the isopropyl group in a wider temperature interval. The rate constants of the isopropyl rotation between syn and anti conformers were determined and the corresponding energy barriers (14–17 kcal/mol) were calculated. DFT calculations of the energy barriers in carvacrol derivatives allowed the determination of the steric origin of the restricted isopropyl rotation. The barrier height depends on the size of the 2- and 4-position substituents, and is independent of the derivatization of the OH group.

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Conformation Analysis and Stereodynamics of Symmetrically ortho-Disubstituted Carvacrol Derivatives

Đorđević Zlatković,

Radulović,

Dangalov

et al. 2024

Molecules

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show abstract

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Ring-fused hexahydro-1,2,4,5-tetrazines: synthesis, structure, and mechanistic studies on isolable rotational isomers

Abstract: We designed conformationally stable rotational isomers around the C(sp2)-C(sp3) axis at the C3-position of hexahydro-1,2,4,5-tetrazines. Isolation of each rotamer by silica gel column chromatography was successfully achieved at room temperature....

Cited by 1 publication

References 47 publications

Conformation Analysis and Stereodynamics of Symmetrically ortho-Disubstituted Carvacrol Derivatives

Conformation Analysis and Stereodynamics of Symmetrically ortho-Disubstituted Carvacrol Derivatives

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