Intramolecular H-bonding interaction in angular 3-π-EWG substituted imidazo[1,2-a]pyridines contributes to conformational preference

Chemistry Central Journal

Manuel Velázquez-Ponce³  Héctor Salgado-Zamora⁴  Hugo A Jiménez-Vázquez⁴  Maria Elena Campos-Aldrete⁴  Rogelio Jiménez⁴  Humberto Cervantes²  Taibi Ben Hadda¹ 

[1] Université Mohammed Premier, Faculté des Sciences, Laboratoire Chimie Matériaux, Oujda, 60000, Morocco

[2] Área de Química, Universidad Autónoma Metropolitana-Unidad Azcapotzalco, Mexico, DF, 02200, México

[3] Departamento de Formación Básica Disciplinaria, Unidad Profesional Interdisciplinaria de Ingeniería Campus Guanajuato, Instituto Politécnico Nacional, Silao de la Victoria-Guanajuato, 36275, Mexico

[4] Departamento de Química Orgánica, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Mexico, DF, 11340, Mexico

关键词: Conformational preference;    Hydrogen bonding;    Peri effect;    Imidazo[1,2-a]pyridine;   

Others  :  787972
DOI  :  10.1186/1752-153X-7-20

 received in 2012-08-15, accepted in 2013-01-17,  发布年份 2013

【 摘 要 】

Background

The proton at position 5 of imidazo[1,2-a]pyridines substituted with an angular electron withdrawing group (EWG) at position 3, shows an unusual downfield chemical shift, which is usually explained in terms of a peri effect. However usage of this term is sometimes confusing. In this investigation, it is proposed that the aforementioned shift is in fact a combination of several factors: Anisotropy, long-distance mesomerism and an attractive intramolecular interaction of the electrostatic hydrogen bond type.

Results

Theoretical calculations were performed aimed to obtain evidence of the existence of an intramolecular non-bonding interaction between H-5 and the oxygen atom of the EWG. Results derived from conformational and vibrational analysis at the DFT B3LYP/6-311++G(d,p) level of theory, the determination of Bond Critical Points derived from AIM theory, and the measurement of some geometrical parameters, support the hypothesis that the higher stability of the prevailing conformation in these molecules (that in which the oxygen of the EWG is oriented towards H-5) has its origin in an intramolecular interaction.

Conclusion

Computational calculations predicted correctly the conformational preferences in angular 3-π-EWG-substituted imidazo[1,2-a]pyridines. The existence of an electrostatic hydrogen bond between H-5 and the oxygen atom of the π-EWG was supported by several parameters, including X-ray crystallography. The existence of such structural array evidently impacts the H-5 chemical shift.

【 授权许可】

   
2013 Velázquez-Ponce et al.; licensee Chemistry Central Ltd.

【 图 表 】

Figure 1.

Scheme 1

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Scheme 2

Figure 3.

Scheme 3

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Scheme 4

Figure 5.

Scheme 5

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Figure 9.

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