2‐Desoxy‐Zucker, V. Digitoxigenin‐2‐desoxy‐β‐<scp>D</scp>‐allopyranosid

Zorbach, W. Werner; Bühler, Wolfgang

doi:10.1002/jlac.19636700116

Cited by 6 publications

(5 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Much of the work in the ensuing decades focused on the use of deoxyglycoside bromides for the preparation of nucleoside analogues, , or thioglycosides . Two early reports describing the use (or attempted use) of 2-deoxyglycosyl halides in O -glycoside synthesis emerged in the early 1960s from Zorbach and co-workers during early synthetic studies on digitoxin. , Here the authors demonstrated that reacting 1-bromo-2-deoxy-3,4,6-tri- O - p -nitrobenzolyl ribopyranose 9 with digitoxigenin 10 , followed by removal of the p -nitrobenzoyl (PNB) protecting groups, afforded the desired digitoxin derivative 11 in 46% as a single β-anomer (Scheme ).…”

Section: Direct Synthesismentioning

confidence: 99%

Methods for 2-Deoxyglycoside Synthesis

2018

View full text Add to dashboard Cite

Deoxy-sugars often play a critical role in modulating the potency of many bioactive natural products. Accordingly, there has been sustained interest in methods for their synthesis over the past several decades. The focus of much of this work has been on developing new glycosylation reactions that permit the mild and selective construction of deoxyglycosides. This Review covers classical approaches to deoxyglycoside synthesis, as well as more recently developed chemistry that aims to control the selectivity of the reaction through rational design of the promoter. Where relevant, the application of this chemistry to natural product synthesis will also be described.

show abstract

Section: Direct Synthesismentioning

confidence: 99%

Methods for 2-Deoxyglycoside Synthesis

2018

View full text Add to dashboard Cite

show abstract

“…4-Amino-l-(2-deoxy-6-0 -phosphono-/?-D-,rjfeo -hexopyranosyl)-2-pyrimidinone, Ammonium Form (29). 4-Amino-1-(2-deoxy-d-D-nbo-hexopyranosyl)-2-pyrimidinone (13) was treated in the same manner as described for the synthesis the AMP analogue 27, but the reaction was terminated after 2.5 h and the overall yield of 29 was 83%: 4H NMR (Me2SO-d6) 7.58 (d, 1, CgH, J = 7.18 Hz), 7.26 (s, 2, NH2, exchanged with D20), 5.99 (m, 1, CVH), 5.84 (d, 1, C5H, J = 7.18 Hz), and other sugar protons; 31P NMR (D20, pH 11.0) 6.73 (s).…”

Section: Methodsmentioning

confidence: 99%

“…Cl' 7887 (2) 1511 (3) 7134 ( 5) 26 (1) C2' 7650 (3) 583 (3) 5941 ( 5) 32 (1) C3' 6611 (2) 375 (3) 5734 ( 5) 29 standard deviation values are in parentheses. 6 Hydrogen atoms for which parameters were calculated are omitted.…”

Section: Conformation and Anomeric Configurationmentioning

confidence: 99%

Synthesis, structure, and biological activity of certain 2-deoxy-.beta.-D-ribo-hexopyranosyl nucleosides and nucleotides

Nord¹,

Dalley²,

McKernan³

et al. 1987

J. Med. Chem.

View full text Add to dashboard Cite

2-Deoxy-beta-D-ribo-hexopyranosyl nucleosides with adenine (2), hypoxanthine (17), guanine (23), cytosine (13), and uracil (7) as the aglycon were synthesized by the Lewis-acid catalyzed condensation of an appropriate trimethylsilylated heterocyclic base and 2-deoxy-1,3,4,6-tetrakis-O-(4-nitrobenzoyl)-beta-D-ribo-hexopyranose+ ++ (5) to provide the desired beta anomers in good yield. When the synthesis of 7 via an SN2 displacement was attempted by reaction between silylated uracil and 2-deoxy-3,4,6-tris-O-(4-nitrobenzoyl)-alpha-D-ribo-hexopyranosyl bromide (8), the major product, 1-(2-deoxy-3,4,6-tris-O-(4-nitrobenzoyl)-alpha-D-ribo-hexopyranosyl)-2,4 - pyrimidinedione (9), had retained the alpha configuration at the anomeric carbon. The structures of both anomers of 1-(2-deoxy-D-ribo-hexopyranosyl)-2,4-pyrimidinedione were assigned by single-crystal X-ray methods. The anomeric configuration and conformation of other nucleosides were determined by proton magnetic resonance analysis of the 4-nitrobenzoylated nucleosides. Nucleoside 6'-monophosphates of 7, 13, and 2 and the 4',6'-cyclic monophosphate of 2 were also prepared. All 2'-deoxy-D-ribo-hexopyranosyl nucleosides and 6'-monophosphate derivatives were tested in vitro for antiviral and antitumor activity. The guanosine analogue 23 was moderately active against HSV-2 virus. The UMP analogue, 1-(2-deoxy-6-O-phosphono-beta-D-ribo-hexopyranosyl) -2,4-pyrimidinedione (28), demonstrated moderate activity against HSV-2 and parainfluenza 3 virus and was also active against L1210 (ID50 = 39 microM) and P388 (ID50 = 33 microM) leukemic cell lines. Two compounds, 6-amino-9-(2-deoxy-beta-D-ribo-hexopyranosyl)purine (2) and 9-(2-deoxy-beta-D-ribo-hexopyranosyl)-2,6-diaminopurine (24), were substrates for adenosine deaminase (EC 3.5.4.4) with Km values of 57 and 90 microM, respectively. 6-Amino-7-(2-deoxy-beta-D-ribo-hexopyranosyl)purine, 18, was a competitive inhibitor of ADase (Ki = 0.1 mM).

show abstract

“…spectrum showed resonances at y 4.13 (C-l doublet, J = 3.5 c.p.s. ), 6.11 (benzylthio singlet), 6.45 (C-6, 2 proton quartet), 6.85 (C-5, one proton multiplet), 8.58 and 8.73 (isopropylidene methyls). Anal.…”

mentioning

confidence: 99%

“…30-60°), affording 0.065 g. of crystals, m.p. 165-166°; [a]24 + 54.5°( 1%); JC»1 2.99, 3.02 and 6.42 (NH), and 5.68 (O-acetyl C=0), 6.02 µ (amide C=0); there was no appreciable absorption near 5.90 µ, suggestive of an S-acetyl carbonyl, nor near 7.40 µ, suggestive of the methyl group of the S-acetate. The n.m.r.…”

mentioning

confidence: 99%