Total synthesis of dapiramicin B

Ohno, Hiroyuki; Terui, Takashi; Kitawaki, Takafumi; Chida, Noritaka

doi:10.1016/j.tetlet.2006.06.001

Cited by 14 publications

(8 citation statements)

References 26 publications

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“…The total synthesis of Dapiramicin B was reported employing Buchwald−Hartwig coupling between the aminodisaccharide and 2-bromopyrrolo[2,3-d]pyrimidine as a key reaction. 123 Nucleoside Q (307, Scheme 60) is a natural hypermodified nucleoside and is widely distributed in the anticodon stem loop of tRNAs. 124 To achieve its synthesis, D-(−)-ribose (−)-261 was protected as acetonide and oxidized with an excess of PCC to reach monomethylacetal 298.…”

Section: Natural Products and Derivativesmentioning

confidence: 99%

Synthetic Entries to and Biological Activity of Pyrrolopyrimidines

et al. 2015

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This review summarizes recent literature (2000-2015) on the synthesis and pharmaceutical properties of pyrrolopyrimidines. These modified pyrimidine bases, fused to a pyrrole ring, and their corresponding nucleosides display a broad applicability in medicinal chemistry. This overview is divided into three main sections, according to the respective isomers: pyrrolo[2,3-d]pyrimidines, pyrrolo[3,2-d]pyrimidines, and pyrrolo[3,4-d]pyrimidines. Each section contains a description of common retro-synthetic strategies, with particular attention for newly reported synthetic entries to the scaffold. Next, the synthetic strategies and the ways in which the scaffolds can be further modified are exemplified according to the biological properties of the obtained products.

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Section: Natural Products and Derivativesmentioning

confidence: 99%

Synthetic Entries to and Biological Activity of Pyrrolopyrimidines

et al. 2015

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“…Dapiramicin A ( 3 ) represents a nucleoside related molecule with an unusual glycosylation site. Here, the sugar moiety is linked to the amino group of the 7-deazapurine base …”

mentioning

confidence: 99%

Glycosylation of Pyrrolo[2,3-d]pyrimidines with 1-O-Acetyl-2,3,5-tri-O-benzoyl-β-d-ribofuranose: Substituents and Protecting Groups Effecting the Synthesis of 7-Deazapurine Ribonucleosides

2018

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Glycosylation of nonfunctionalized 6-chloro-7-deazapurine with commercially available 1- O-acetyl-2,3,5-tri- O-benzoyl-β-d-ribofuranose (45%) followed by amination and deprotection gave tubercidin in only two steps. Similar conditions applied for the synthesis of 7-deazaguanosine employing pivaloylated 2-amino-6-chloro-7-deazapurine gave 18% glycosylation yield. The less bulky isobutyryl or acetyl protected amino group directed the glycosylation toward the exocyclic amino substituent. 7-Halogenated intermediates were glycosylated followed by dehalogenation to overcome the low glycosylation yield in the synthesis of 7-deazaguanosine.

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“…Evidence for the natural occurrence of methylated prequeuosine bases stems from a recent study that demonstrated that m 6 preQ 0 is produced by Streptomyces [ 17 ]. Moreover, the natural products huimycin [ 18 ] and dapiramicin contain m 6 preQ 0 as core with their 2-NH 2 group linked to a 2'-acetamido-2'-deoxy-ß-ᴅ-glucopyranosyl residue in huimycin and to a 2-[4'-(4''- O -methyl-ß-ᴅ-glucopyranosyl)-6'-deoxy-α-ᴅ-glucopyranosyl] moiety in dapiramicin A [ 19 – 20 ]. In the biosynthetic pathway, the conversion of preQ 0 into huimycin requires methylation of preQ 0 and attachment of the N -acetylglucosamine moiety as final steps [ 18 ].…”

Section: Resultsmentioning

confidence: 99%

“…We further optimized this path for the synthesis of 15 N-labeled prequeuosine nucleobase derivatives [ 26 ] required for advanced NMR spectroscopic applications [ 27 ], and for the syntheses of azido- or amino-functionalized preQ 1 derivatives needed for cellular applications with engineered riboswitches [ 28 ]. Finally, we point out that only a single synthetic route has been published to a potential O 6 -methylated precursor of m 6 preQ 1 , namely N 9-trimethysilylethyl protected m 6 preQ 0 [ 20 ]. This synthesis, however, is based on methylation using diazomethane resulting in a mixture of N 1 and O 6 methylated products, and we therefore did not further consider this path.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of O⁶-alkylated preQ₁ derivatives

Flemmich

Moreno

Micura

2021

Beilstein J. Org. Chem.

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A naturally occurring riboswitch can utilize 7-aminomethyl-O6-methyl-7-deazaguanine (m6preQ1) as cofactor for methyl group transfer resulting in cytosine methylation. This recently discovered riboswitch-ribozyme activity opens new avenues for the development of RNA labeling tools based on tailored O6-alkylated preQ1 derivatives. Here, we report a robust synthesis for this class of pyrrolo[2,3-d]pyrimidines starting from readily accessible N2-pivaloyl-protected 6-chloro-7-cyano-7-deazaguanine. Substitution of the 6-chloro atom with the alcoholate of interest proceeds straightforward. The transformation of the 7-cyano substituent into the required aminomethyl group turned out to be challenging and was solved by a hydration reaction sequence on a well-soluble dimethoxytritylated precursor via in situ oxime formation. The synthetic path now provides a solid foundation to access O6-alkylated 7-aminomethyl-7-deazaguanines for the development of RNA labeling tools based on the preQ1 class-I riboswitch scaffold.

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Total synthesis of dapiramicin B

Cited by 14 publications

References 26 publications

Synthetic Entries to and Biological Activity of Pyrrolopyrimidines

Synthetic Entries to and Biological Activity of Pyrrolopyrimidines

Glycosylation of Pyrrolo[2,3-d]pyrimidines with 1-O-Acetyl-2,3,5-tri-O-benzoyl-β-d-ribofuranose: Substituents and Protecting Groups Effecting the Synthesis of 7-Deazapurine Ribonucleosides

Synthesis of O⁶-alkylated preQ₁ derivatives

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Total synthesis of dapiramicin B

Cited by 14 publications

References 26 publications

Synthetic Entries to and Biological Activity of Pyrrolopyrimidines

Synthetic Entries to and Biological Activity of Pyrrolopyrimidines

Glycosylation of Pyrrolo[2,3-d]pyrimidines with 1-O-Acetyl-2,3,5-tri-O-benzoyl-β-d-ribofuranose: Substituents and Protecting Groups Effecting the Synthesis of 7-Deazapurine Ribonucleosides

Synthesis of O6-alkylated preQ1 derivatives

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Synthesis of O⁶-alkylated preQ₁ derivatives