Synthesis of nucleoside derivatives via heterocyclocondensation reactions

Kikelj, Vincent; Setzer, Paul; Julienne, Karine; Meslin, J. C.; Deniaud, David

doi:10.1016/j.tetlet.2008.03.069

Cited by 5 publications

(4 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Furthermore, we have also published the synthesis of different non‐natural N ‐glycosyl pyrimidines. Furanosides, pyranosides, as well as disaccharides were isolated . Perbenzoylated ribofuranoside 2 and peracetylated glucopyranoside 3 represent this class of targeted and isolated pyrimidines (Figure ).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Approach to Artificial Nucleosides from Glycoside Isothiocyanates: Synthesis of Original N‐Glycosylated Heterostructures by Cyclocondensation Reactions

et al. 2019

Self Cite

View full text Add to dashboard Cite

Unusual purine nucleoside analogues were synthesized, using the well‐tried methodology in heterocyclic chemistry. This result expands the scope of accessible N‐glycosylated heterocyclic structures. Pyrimidine, and bicyclic pyrimido[1,2‐a]pyrimidine nucleoside analogues were prepared from common glycoside isothiocyanate precursors. Key cyclization steps were all based on a cyclocondensation reaction involving an activated heterodienic chain. Finally, thirteen pyrimido[1.2‐a]pyrimidine nucleoside analogues 13 a‐m were synthesized with a 30% yield on average, over 8 or 9 steps from one of the isothiocyanates 4 a‐c. These elaborated targets were fully characterized.

show abstract

Section: Introductionmentioning

confidence: 99%

“…Furanosides, pyranosides, as well as disaccharides were isolated. [11][12][13] Perbenzoylated ribofuranoside 2 and peracetylated glucopyranoside 3 represent this class of targeted and isolated pyrimidines ( Figure 2).…”

Section: Introductionmentioning

confidence: 99%

Approach to Artificial Nucleosides from Glycoside Isothiocyanates: Synthesis of Original N‐Glycosylated Heterostructures by Cyclocondensation Reactions

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…Synthetic exocyclic amino nucleosides, like ribofuranosylamino pyrimido[5,4‐d]pyrimidine, show antitumor and antiviral properties . Other glucosylamino pyrimidines , triazines , thiazoles , and triazoles , with various activities, have also been reported. Classically, these exocyclic amino nucleosides are prepared by a condensation reaction of glycosylamine derivatives with chloronucleobases or by coupling silylated aminoheterocycles with peracetylated glycosides .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Thiadiazolylaminoglycosides Through Ring Contraction of Triazinoglycosides Induced by [TBA‐Ox]

Kikelj

Julienne

Chalopin

et al. 2014

Journal of Heterocyclic Chem

Self Cite

View full text Add to dashboard Cite

show abstract

“…We recently published the synthesis of pyrimidic nucleoside analogues from a glucosyldiazadiene and acylchlorides in a regioselective hetero-cyclocondensation reaction. 3 We are now targeting access to new nucleoside analogues bearing more complex and original heterocyclic bases. Such novel compounds could be generated by further elaboration of the available pyrimidic analogues through the introduction of various substituents on the pyrimidinone ring.…”

mentioning

confidence: 99%

Concerning the Nucleophilic Displacement of a Methylsulfanyl Group on Substituted Pyrimidinones

Kikelj¹,

Grosjean²,

Meslin³

et al. 2010

Synthesis

Self Cite

View full text Add to dashboard Cite

The nucleophilic displacement of a methylsulfanyl group (SMe) at the C2-position on a pyrimidin-4-one scaffold was achieved after oxidation into a methylsulfonyl group (SO 2 Me) using dimethyldioxirane (DMDO), a powerful electrophilic oxygen atom transfer agent. The introduction of amino groups as well as formation of carbon-carbon bonds was thus demonstrated.During the course of our investigations on heterocyclic chemistry, 1,2 we became interested in the nucleophilic displacement of a methylsulfanyl group on a pyrimidinone skeleton. We recently published the synthesis of pyrimidic nucleoside analogues from a glucosyldiazadiene and acylchlorides in a regioselective hetero-cyclocondensation reaction. 3 We are now targeting access to new nucleoside analogues bearing more complex and original heterocyclic bases. Such novel compounds could be generated by further elaboration of the available pyrimidic analogues through the introduction of various substituents on the pyrimidinone ring. It appeared clear that the presence of the methylsulfanyl group on the heterocycle could help achieve this goal.Here, we report on studies undertaken with the model substrate 1 into the generation of a nonglycosidic series. Pyrimidinone 1 was prepared according to our heterocyclocondensation methodology by employing an activated 1,3-diazabutadienic building block (Scheme 1). 4 The heterodiene, which was obtained in three steps from phenylthiourea in quantitative yield, was condensed with phenylacetyl chloride in the presence of triethylamine to afford compound 1 in 90% yield. Scheme 1 Preparation of model substrate 1 for methylsulfanyl group displacement studiesThe methylsulfanyl substituent is located at the C2-position of the pyrimidin-4-one 1. It is worth noting the high difference in reactivity compared to the case of a C4-positioned substituent on a pyrimidin-2-one scaffold. Indeed, we have previously published the direct and easy modification of 4-methylsulfanylpyrimidin-2-ones (Scheme 2). 5 Nucleophilic displacements of the sulfanyl group were achieved in good yields with hydrogen sulphide in basic medium or potassium hydroxide in alcoholic medium. Other nucleophiles such as sodium alkoxides or amines were also used with success on pyrimidine-2-thiones. However, these substitution reactions were limited to heteroatomic nucleophiles. Indeed, attempts at the introduction of a carbon-carbon bond failed.Scheme 2 Modulation of 4-methylsulfanylpyrimidin(e)-2-(thi)ones by direct substitution of the sulfanyl group Additionally, we hoped to effect substitution of the C2-sulfanyl of pyrimidin-4-one 1. We were therefore disappointed to observe the very weak reactivity of this substrate, particularly towards nitrogenous nucleophiles. Only the hydroxide anion could, under severe conditions (high temperatures and extended reaction times), generate the corresponding carbonyl derivative 2 through substitution and prototropic equilibrium. This difficulty is hardly mentioned in the literature, even for reactions at the C2-position on pyrimidine r...

show abstract

Synthesis of nucleoside derivatives via heterocyclocondensation reactions

Cited by 5 publications

References 35 publications

Approach to Artificial Nucleosides from Glycoside Isothiocyanates: Synthesis of Original N‐Glycosylated Heterostructures by Cyclocondensation Reactions

Approach to Artificial Nucleosides from Glycoside Isothiocyanates: Synthesis of Original N‐Glycosylated Heterostructures by Cyclocondensation Reactions

Synthesis of Thiadiazolylaminoglycosides Through Ring Contraction of Triazinoglycosides Induced by [TBA‐Ox]

Concerning the Nucleophilic Displacement of a Methylsulfanyl Group on Substituted Pyrimidinones

Contact Info

Product

Resources

About