Nucleic acid related compounds. 27. "Virtual coupling" of the anomeric proton of cyclic 2'-deoxynucleoside 3',5'-monophosphates. Reassessment of conformation using praseodymium shifts and assignment of H-2',2 signals by biomimetic deuteration at C-2'

Robins, Morris J.; MacCoss, Malcolm; Wilson, John S.

doi:10.1021/ja00456a023

Cited by 24 publications

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The 3',5'-dichloro-2',3,,5'-trideoxynucleosides prepared from the parent 2'-deoxyribonucleosides with thionyl chloride in hexamethylphosphoramide were dehydrochlorinated to their corresponding diolefinic nucleosides. Treatment of 9-(3,5-dichloro-2,3,5-trideoxy-/3-D-threo-pentofuranosyl)adenine (1) with dilute sodium hydroxide in ethanol gave the endocyclic diolefinic nucleoside 9-[2-(5-methylfuryl)]adenine (11). In contrast, similar treatment of 1-(3,5-dichloro-2,3,5-trideoxy-/3-D-threo-pentofuranosyllthymine (3) and the corresponding uracil derivative (4) afforded the exocyclic diolefinic nucleosides 2-methylene-5(fl)-(thymin-l-yl)-2,5-dihydrofuran (8) and 2methylene-5(fi)-(uracil-l-yl)-2,5-dihydrofuran (9).

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“…Various synthetic approaches have been used to introduce endo-and exocyclic unsaturation into the sugar moiety of both purine and pyrimidine nucleosides.2 For instance, Robins and co-workers3•4 recently reported the preparation of the three possible endocylic unsaturated nucleosides derived from adenosine as well as the 2',3' and 3',4' olefinic nucleosides derived from tubercidin. The syntheses of the exocyclic 4',5'-unsaturated nucleosides derived from adenosine and from the pyrimidine nucleosides have been described by Moffatt and colleagues.5 •6 The endocyclic diolefinic nucleosides 1 -[2-(5-methylfuryl)]thymine (13) and 9-[2-(5-methylfuryl)] adenine (11) have been prepared by Horwitz et al 7 and McCarthy and co-workers8 from 3',5'-di-0-mesylthymidine and 5'-S-ethyl-3'-0-tosyl-5'-thio-2,,5,-dideoxyadenosine, respectively, via base-catalyzed double-elimination reactions. On the other hand, dehydrohalogenation of 3',5'-dideoxy-3',- 5'-diiodothymidine with silver fluoride in pyridine or of 1-(2,3,5-trideoxy-5-iodo-/3-D-gfycero-pent-2-enofuranosyl)thymine with l,5-diazabicyclo[4.3.0]non-4-ene in acetonitrile yielded the exocyclic diolefinic nucleoside 2-methylene-5(fí) -(thymin-l-yl) -2,5-dihydrofuran (8).…”

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Dehydrohalogenation of some 3',5'-dichloro-2',3',5'-trideoxynucleosides

Yueh¹,

Hogenkamp²

1978

J. Org. Chem.

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Dehydrohalogenation of some 3',5'-dichloro-2',3',5'-trideoxynucleosides

Yueh¹,

Hogenkamp²

1978

J. Org. Chem.

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ChemInform Abstract: NUCLEIC ACID RELATED COMPOUNDS. 27. ′VIRTUAL COUPLING′ OF THE ANOMERIC PROTON N OF CYCLIC 2′‐DEOXYNUCLEOSIDE 3′,5′‐MONOPHOSPHATES. REASSESSMENT OF CONFORMATION USING PRASEODYMIUM SHIFTS AND ASSIGNMENT OF H‐2′,2 SIGNALS BY BIOMIMETIC DEUTERATION AT C‐2′

Robins¹,

MacCoss²,

Wilson³

1977

Chemischer Informationsdienst

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Empirical Correlations Between Conformational Parameters in β‐D‐Furanoside Fragments Derived from a Statistical Survey of Crystal Structures of Nucleic Acid Constituents Full Description of Nucleoside Molecular Geometries in Terms of Four Parameters

Leeuw

Haasnoot

Altona

1980

Israel Journal of Chemistry

255

135

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A data file was created containing internal coordinates and derived parameters for 178~-D-furanoside fragments, occurring in X-ray structures of ribo-, 2'-deoxyriboand arabinonucleoside derivatives. The variability in bond angles and torsion angles can be described by four conformational parameters; the kind and degree of ring puckering as expressed in phase angle of pseudorotation P and puckering amplitude " m , the conformation of the side-chain 0 and the glycosidic torsion angle X. Comparison between out-of-plane and torsion angle methods for calculation of pseudorotation parameters revealed that the latter method is better suited to describe the internal coordinates of the non-equilateral five-membered ring. Inspection of the distribution of phase angles and puckering amplitudes lends additional support to the hypothesis that conformational interconversion of the familiar Nand S type ring conformers is a process of hindered pseudorotation, proceeding through the 04'endo conformation (P = 90°) and maintaining a constant puckering amplitude. Both syn-anti distribution and preferred ranges of X are correlated with furanose conformation in ribonucleosides; the distribution is also affected by the type of base, purines showing higher syn/anti ratios than pyrimidines. Three modes are observed for the backbone torsion angle 0(C4'-C5'); the most abundant rotamer is 0., followed by 0•. The O. rotamer has so far been found only in S-type furanosides. Regressions based on existing or modified equations were used to express variations in internal coordinates in terms of the four parameters involved. As a consequence of its anomeric character, the glycosidic bond length can be described by a cyclic function of X. Endocyclic bond angles' and torsion angles show small but systematic deviations from the pseudorotation equations derived for equilateral rings. Based on observed correlations with the four parameters, reasonably accurate coordinates for exocyclic atoms, including hydrogen atoms, could also be obtained. Coordinates for model {3-D-furanoside fragments with preferred X and 0 orientations and variable pseudorotation parameters, covering a part of the N;:= S interconversion pathway, are presented. Their usefulness in future theoretical and experimental studies on nucleic acid conformations, both in the solid state and in solution, is discussed.• This paper is part XIII in the series Nucleic Acid Constituents from this laboratory. For part XII sec Nature, 281, 235 (1<)79).

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Nucleic acid related compounds. 27. "Virtual coupling" of the anomeric proton of cyclic 2'-deoxynucleoside 3',5'-monophosphates. Reassessment of conformation using praseodymium shifts and assignment of H-2',2 signals by biomimetic deuteration at C-2'

Cited by 24 publications

References 4 publications

Dehydrohalogenation of some 3',5'-dichloro-2',3',5'-trideoxynucleosides

Dehydrohalogenation of some 3',5'-dichloro-2',3',5'-trideoxynucleosides

ChemInform Abstract: NUCLEIC ACID RELATED COMPOUNDS. 27. ′VIRTUAL COUPLING′ OF THE ANOMERIC PROTON N OF CYCLIC 2′‐DEOXYNUCLEOSIDE 3′,5′‐MONOPHOSPHATES. REASSESSMENT OF CONFORMATION USING PRASEODYMIUM SHIFTS AND ASSIGNMENT OF H‐2′,2 SIGNALS BY BIOMIMETIC DEUTERATION AT C‐2′

Empirical Correlations Between Conformational Parameters in β‐D‐Furanoside Fragments Derived from a Statistical Survey of Crystal Structures of Nucleic Acid Constituents Full Description of Nucleoside Molecular Geometries in Terms of Four Parameters

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