Nucleophilic displacement reactinos with thiobenzoate. New syntheses of deoxy-thioadenosine derivatives starting from adenosine.

Mengel, Rudolf; Grießer, Helmut

doi:10.1016/s0040-4039(01)92863-1

Cited by 16 publications

(13 citation statements)

References 8 publications

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“…31 Besides, small optical rotations are difficult to measure accurately. We thus can conclude that only for larger ORs {[20 deg[dm(g/ cm 3 )]…”

Section: Energeticsmentioning

confidence: 94%

“…[1][2][3] Many of them can be biologically active. Several amino derivatives are precursors for antibiotics 4 or drugs for antiradiation treatment.…”

Section: Introductionmentioning

confidence: 99%

“…Mean average deviation (MAD) of calculated values from the experiment was $53 deg[dm(g/cm 3 )] 21 for the B3LYP functional populations. The error is higher for MP2 populations, because of the error in energy of the gg conformer of 1.…”

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confidence: 99%

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Conformational behavior of simple furanosides studied by optical rotation

Kaminský¹,

Raich²,

Tomčáková³

et al. 2010

J Comput Chem

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Experimental and theoretical specific optical rotations (OR) of anhydro, epithio, and epiminoderivatives of methyl tetrofuranosides in chloroform solutions have been compared and used as a tool for exploring their conformational behavior. The potential energy surfaces of these saccharides with reduced flexibility were examined with the density functional theory and the MP2 and CCSD(T) wavefunctions methods. Theoretical ORs were obtained by Boltzmann averaging of values calculated for local minima. Resultant rotations could be used to assess the quality of the DFT and MP2 relative conformer energies. OR values calculated for equilibrium geometries in vacuum were significantly improved when the solvent was accounted for by a polarizable continuum model and first and diagonal second OR derivatives were used for an anharmonic vibrational averaging. The DFT used as a default method reproduced the experimental data fairly well. A modified B3LYP functional containing 70% of HF exchange further improved the results. Because of the strong dependence of OR on the conformation, not only the absolute configuration could be determined, but also the conformational populations were estimated. Likewise, the predicted dependence of OR on the light wavelength well agreed with experiment. The increasing precision of the contemporary computational methods thus makes it possible to relate the specific rotation to more detailed features in molecular structure.

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“…31 Besides, small optical rotations are difficult to measure accurately. We thus can conclude that only for larger ORs {[20 deg[dm(g/ cm 3 )]…”

Section: Energeticsmentioning

confidence: 94%

“…[1][2][3] Many of them can be biologically active. Several amino derivatives are precursors for antibiotics 4 or drugs for antiradiation treatment.…”

Section: Introductionmentioning

confidence: 99%

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Conformational behavior of simple furanosides studied by optical rotation

Kaminský¹,

Raich²,

Tomčáková³

et al. 2010

J Comput Chem

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“…0341-0382/79/1200-1075 $01.00/0 2'-thiobenzoyl-2'-deoxyadenosine (2'-BSA), 3'-thio-3'-deoxyadenosine (3'-HSA) [7]; 2'-chloro-2'-de- [11]; S'-amino-S'-deoxyadenosine (S'-NHaA), 5'-acido-5'-deoxyadenosine (5'-N 3A) [12]; and 5'-chloro-5'-deoxyadenosine (5'-ClA) [13] were prepared as described in previous publications.…”

Section: Sample Preparationmentioning

confidence: 99%

Ribose Conformations of Adenosine Analogs Modified at the 2', 3' or 5' Positions

Klimke

Cuno

Lüdemann

et al. 1979

Zeitschrift Für Naturforschung C

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The solution conformation of adenosine(β)ribosides modified at the 2′, 3′ or 5′ position is derived from the analysis of the HRNMR spectra of the ribose protons. The conformational equilibria of the furanoside rings are described by the two state N ↔ S model introduced by Altona and Sundaralingam. The new compounds studied are: 2′-thiobenzoyl-2′-deoxyadenosine, 3′-thio-3′-deoxyadenosine, 2′-chloro-2′-deoxyadenosine, 3′-chloro-3′-deoxyadenosine, 2′-bromo- 2′-deoxyadenosine, 3′-bromo-3′-deoxyadenosine, 2′-O-methyladenosine, 3′-O-methyl-adenosine, 2,-deoxy-3,-O-methyladenosine, 5′-amino-5′-deoxyadenosine, 5′-acido-5′-deoxyadenosine, and 5′-chloro-5′-deoxyadenosine. The emphasis in this work is to study systematically the influence of the different substituents upon the conformational equilibria of the sugar. It is found that any substitution at the 2′ position stabilizes the S-conformer. An even more pronounced stabilization of the A-conformer in the 3′ substituted analogs is observed. The equilibrium changes in these classes of compounds can neither be correlated quantitatively with electronegativity differences nor with sterical differences between the various substituents. Substitution at the 5′ position influences the N ↔ S equilibrium only slightly, but has significant effects upon the conformational preferences of the exocyclic 5′-CH2R3 group.

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“…Synthesis of 3'-thioadenosine [21], 3'-thiouridine [10], and 3'-thioinosine [2] [22] starting from preformed nucleosides has been reported. So far, this approach has not been applied to the synthesis of 3'-thioguanosine.…”

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confidence: 99%