SnCl4 versus TiCl4-mediated coupling between N-6-benzoyladenine and perbenzoylated 2-deoxypyranose: Application to the synthesis of certain homochiral acyclo and carboacyclonucleosides

Baud, M. V.; Chavis, C.; Lucas, Marc; Imbach, Jean-L.

doi:10.1016/s0040-4020(01)96048-x

Cited by 17 publications

(1 citation statement)

References 20 publications

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“…4'-0-Deprotection of 22 (1.27 g) (prepared by coupling ABz with 13) was carried out exactly as described for the cytidine analogue 19. Flash chromatography (CH2C12-MeOH, 20:2.2) furnished 0.20 g of the less polar a anomer 36 and 0.25 g of the ß anomer 35 ( :ß (2',3'-Dideoxy-/8-D-giycero-pent-2'-enopyranosyl)thymine (43) and a Anomer 44. Deprotection of 28 as described for 41 and 42 followed by flash chromatography (CH2C12-MeOH, 20:1.3) gave a small amount of the less polar a anomer 44. Complete separation was possible using HPLC. Spectroscopic properties of the ß anomer 43 are identical with those of the compound obtained in a stepwise procedure starting from (2',3',4'-tri-0-acetyl-/?-D-xylopyranosyl)uracil.65 44: mp 178-180 °C (crystallized MeOH-CH2Cl2) [lit.32 mp 171 °C (MeOH)]; NMR (DMSO-d6) 11.37 (1H, s), 7.46 (1H, q, J6-ch3 = 1.1 Hz), 6.26 (1H, ddd, J3t = 1.9 Hz, Jar -3.8 Hz, J3-2-= 10.3 Hz), 6.12 (1H, q, Jr2-= Jra-= Jir = 2.0 Hz), 5.76 (1H, ddd, J2-1-= 1.8 Hz, J2r = 0.8 Hz, J2-2-= 10.2 Hz), 5.20 (1H, d, Joh-4-= 6.8 Hz), 3.92 (1H, bs, half-width = 13 Hz), 3.81 (1H, dd, J5-4-= 3.7 Hz, J5-5--= 11.7 Hz), 3.60 (1H, dd, J6-r = 4.0 Hz, J5..5-= 11.7 Hz), (2',3'-Dideoxy-/?-D-gZycero-pent-2'-enopyranosyl)-IVisobutyrylguanosine (45) and a Anomer 46. 6-0-[(p-NitrophenyDethyl] derivative 33 (2.81 g, 6.0 mmol) in dry pyridine (140 mL) and diazabicycloundecene (1.70 mL, 11.3 mmol) was left overnight.…”

Section: Methodsmentioning

confidence: 99%

Easy Synthesis and Different Conformational Behavior of Purine and Pyrimidine .beta.-D-glycero-Pent-2'-enopyranosyl Nucleosides

Doboszewski¹,

Blaton²,

Herdewijn³

1995

J. Org. Chem.

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Section: Methodsmentioning

confidence: 99%

Easy Synthesis and Different Conformational Behavior of Purine and Pyrimidine .beta.-D-glycero-Pent-2'-enopyranosyl Nucleosides

Doboszewski¹,

Blaton²,

Herdewijn³

1995

J. Org. Chem.

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Regioselective Preparation ofN7- andN9-Alkyl Derivatives ofN6-[(Dimethylamino)methylene]adenine Bearing an Active Methylene Group and Their Further Derivatization Leading to α-Branched Acyclic Nucleoside Analogues

Hocková¹,

Budêšínský²,

Marek³

et al. 1999

Eur. J. Org. Chem.

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Synthesis Of Nucleosides

Vorbrüggen¹,

1999

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This chapter deals with the synthesis of nucleosides (e.g., the formation of N ‐glycosides of sugars such as D ‐ribose or 2‐deoxy‐D‐ribose with heterocyclic nitrogen bases). The methods of nucleoside synthesis have been treated in a number of reviews and monographs. It is now generally accepted that nucleosides were among the first organic compounds formed at the start of evolution in the early history of our planet earth. To support this point, guanine and adenine were heated with D ‐ribose in seawater, which contains the Lewis acid magnesium chloride as catalyst. One thus obtained the nucleosides guanosine and adenosine together with comparable yields of unnatural α‐nucleosides. The latter were gradually photoanomerized to the thermodynamically more stable compounds in overall yields of 5–6%. The furanose form of ribose reacts faster than the pyranose form. Corresponding syntheses of the pyrimidine nucleosides uridine and cytidine from uracil , cytosine and ribose are more problematic and remain an enigma. The recent conversion of glycolaldehyde‐ O ‐phosphate and formaldehyde to ribose‐2,4‐di‐ O ‐phosphate might give new insights into the prebiotic syntheses of uridine and cytidine. The evidence and hypotheses for these prebiotic conversions and the evolution of RNA, as well as the implications of an “RNA World,” have been reviewed. These RNA nucleosides are reduced in vivo as 5′‐ O ‐diphosphates by ribonucleotide reductases to the corresponding 2′‐deoxynucleosides—the building blocks of DNA such as 2′‐deoxyguanosine. The thermodynamically controlled synthesis of these four building blocks of RNA has implications for the design of efficient, high yielding, new methods for the synthesis of the naturally occurring nucleosides, nucleoside antibiotics, and modified nucleosides that may serve as antimetabolites to fight viral and parasitic diseases and cancer. The nucleoside rings in this chapter are depicted arbitrarily in the anti conformation, as occurs predominantly in the crystal and solution (based primarily on NOE‐ 1 H‐ and 13 C‐NMR measurements) forms of pyrimidine nucleosides. Only a few nucleosides, such as 6‐methyluridine, occur with the heterocyclic ring predominantly in the syn conformation. The synthesis of C ‐nucleosides has been reviewed previously and is not covered in this review.

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SnCl4 versus TiCl4-mediated coupling between N-6-benzoyladenine and perbenzoylated 2-deoxypyranose: Application to the synthesis of certain homochiral acyclo and carboacyclonucleosides

Cited by 17 publications

References 20 publications

Easy Synthesis and Different Conformational Behavior of Purine and Pyrimidine .beta.-D-glycero-Pent-2'-enopyranosyl Nucleosides

Easy Synthesis and Different Conformational Behavior of Purine and Pyrimidine .beta.-D-glycero-Pent-2'-enopyranosyl Nucleosides

Regioselective Preparation ofN7- andN9-Alkyl Derivatives ofN6-[(Dimethylamino)methylene]adenine Bearing an Active Methylene Group and Their Further Derivatization Leading to α-Branched Acyclic Nucleoside Analogues

Synthesis Of Nucleosides

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