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Conformational analysis of a cyclic nucleotide: 3′−5′-Adenosine monophosphate. A study based on the extended Hückel theory

✍ Scribed by Jean Noël Lespinasse; Dane Vasilescu


Publisher
Wiley (John Wiley & Sons)
Year
1974
Tongue
English
Weight
573 KB
Volume
13
Category
Article
ISSN
0006-3525

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✦ Synopsis


Abstract

The extended Hückel theory (EHT) was used as a quantum mechanical approach for the determination of the best conformation of cyclic AMP. Both geometrical and quantum mechanical studies were necessary to ascertain the configuration of the sugar ring and phosphate ring. This was due to the fact that no crystallographic data are known for the ribose phosphate part of this nucleotide.

The calculations have shown that the sugar ring takes a ^3^T~4~ (C3′‐endo–C4′‐exo) configuration while the phosphate ring exhibits a chair form. Once the geometry of the rigid ribose–phosphate block is resolved, the problem of the determination of the best conformation for cyclic AMP is reduced to the determination of the position of the adenine base with respect to this ribose phosphate part.

The study of the rotation of the adenine base around the glycosidic bond C1′–N9 revealed that the two conformations anti (χ = 30°) and syn (ξ = 210°) are possible with an energy difference of only 1 kcal × mole^−1^. This theoretical calculation is in good agreement with experimental data.