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. 2018 Dec;18(20):1684–1701. doi: 10.2174/1389557518666180516163539

Table 3.

Summary of synthetic adenosine derivatives, methods and physiological action of the last 25 years.

Adenosine Derivatives by Substitution Reactions
Adenosine Derivatives Series Methods of Synthesis and Biological Essay Target Interaction Refs.
C8-amino-N6-disubstitution adenosine Precursors:
• N6-derivative-8-halide adenosine.
• 8-aminoalkyl derivative 6-chloropurine riboside
• 6,8-dichloropurine riboside.
Reaction type: Double selective substitution.
Essay: rat cerebral cortex cells and striated
A1 and A2A receptors [48]
• 2-alkyladenosine
• 2-alkynyl-N6-alkyladenosine.
• Adenosine-5'-N6-ethyluronamide
Precursors:
• 9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-6-chloro-2-iodopurine.
• 2-iodoadenosine
• 2-iodine-N6-alkyladenosine
Reaction type: Double and triple selective substitution.
Essay: Rat ovary cells transfected with human recombinant DNA (adenosine receptors) and platelet.
A2 and A3 receptors [3, 45, 46]
2-Substitution-N6-methyl adenosine. Precursor:
• 9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-6-chloro-2-iodopurine.
Reaction type: Double and triple selective substitution.
A3 receptor [49]
• 2-alkyloxy ether
• 2-alkylaryl
• 2-amino ether
• 2-thioether
Precursor:
• 2-adenosine chlorine.
Reaction type: Nucleophilic substitution.
Essay: Rat ovary cells (CHO)
A3 receptor [50, 51]
• N6-alkyladenosine derivatives Precursor:
• 6-chloropurine riboside.
Reaction type: Nucleophilic substitution.
Essay: Cell lines of bladder carcinoma T24 and J88 types.
Carcinoma cell lines [52]
• N6-biotinyl-8-azidoadenosine probe Precursor:
• Inosine
Reaction type: Nucleophilic substitution.
Essay: Cell lines of bladder carcinoma T24 and J88 types.
Adenosine Deaminasa (cADA) [57]
• 2’-deoxymethylene nucleosides Precursor:
• Guanosine
Reaction type: Nucleophilic substitution;, oxidation by Swern method; methylenation by Wittig reaction and nonaqueous diazotization (substitution reaction)
Essay: Mouse lymphocytic leukemia cell line (L1210)
Ribonucleotide Reductase Enzyme (RNR) [58]
• N-benzylated-7-deazaadenosine analogues Precursor:
• Turbercidin
Reaction type: Alkylation and SNAr
Essay: Murine leukemia (L1210) cellsand human T-lymphocyte (CEM),cervix carcinoma (HeLa), prostateadenocarcinoma (PC-3), andkidney carcinoma (Caki-1) cells, and Nucleoside Transport.
hENT1 and pool cell lines [74]
Adenosine Derivatives by Complexation Reactions
[Ru2(CH3CO2)4(C10H13N5O4)2] Cl Precursor:
• Adenosine.
Reaction type: Complexation reaction
Essay:Growing Escherichia coli.
E. coli bacteria [61]
Adenosine Derivatives by Complexation Reactions
Adenosine Derivatives Series Methods of Synthesis and Biological Essay Target Interaction Refs.
Trans-[PtCl2(N6-(substituted-benzyl) adenosine)2]*Solv.
Trans-[PtCl2(2-chloro-N6-(substituted-benzyl) adenosine)2]*Solv.
Precursor:
• K2[PtCl4]
• 6-chloropurine-9-ribose
• 2,6-dichloropurine-9-ribose.
• Amine derivatives.
Reaction type: Complexation reaction.
Essay: Osteosarcoma (HOS) and breast adenocarcinoma.
Carcinoma cell lines [62, 63]
Adenosine Derivatives by Conjugation and Coupling Reactions
• N6-amino derivatives of adenosine 5'- monophosphate.
• 5'-adenosine phosphoramidate amino derivatives
• 5'-N6-fluorescein derivatives AMP
• 5'- and N6 - biotin derivatives AMP
Precursor:
• Diamines
• AMP
• 6-chloropurine riboside-5-monophosphate.
• 5(6)-carboxifluorescein-N- hydroxysuccinimide ester (FAM-SE).
• Biotin N-hydroxysuccinimide ester (biotin-SE)
Reaction type: Coupling and direct displacement.
Essay: In vitro RNA transcription, Electrophoresis.
RNA [65]
• Folate-adenosine-5'-(13-amino-4,7, 10-trioxa tridecyl) phosphoramidate)
• Folate-adenosine-5'-(6-aminohexyl) phosphoramidate
Precursor:
• AMP, N-methylimidazole and hidrochloruro N-(3-dimethylaminopropyl)-N'-Ethylcarbodiimide (EDC).
• Diamine
• Folic acid.
• NHS
Reaction type: Conjugation.
Essay: RNA sequence in vitro
RNA
• Homologated apio analogues of IB-MECA and Cl-IB-MECA Precursor:
• IB-MECA and Cl-IB-MECA
• Glycosyl donor
• 2,6-dichloropurine
• 3-Halobenzyl amines
Reactions types:
• Controlled oxidative cleavage of vicinal diol.
• Mitsunobu condensation reactions.
Essay: Docking molecular and MM-GBSA.
A3 receptor [69]
• 2,6-diamino-8-azapurine sulfate Precursor:
• Ribose-1-phosphate
• D-aaPur
• α-D-ribose-1-phosphate
• 8-azaguanine
Reactions types: Ribosylation
Essay: Escherichia coli culture and solution purine-nucleoside phosphorylase.
Purine-nucleoside phosphorylase (PNP) and bacteria E.coli [87]
• N6-(2-methoxybenzyl)adenosine (2 OMeL)
• N6-(4-methoxybenzyl)adenosine (4 OMeL)
• N6-(4-methylbenzyl)adenosine (4MeL)
• N6-(2-chlorobenzyl)adenosine (2 ClL)
• N6-(4-fluorobenzyl)adenosine (4 FL)
Precursor:
• N6-benzyladenosine derivative
• K2[Pt(ox)2]·2H2O
Reactions types:
One-step synthetic procedure using the reaction of potassium bis(oxalato)platinate(II)
Essay: Cancer cells (osteosarcoma and breast adenocarcinoma)
Human cancer cell lines [63]
Adenosine Derivatives by Conjugation and Coupling Reactions
Adenosine Derivatives Series Methods of Synthesis and Biological Essay Target Interaction Refs.
• 5’-(N-aminoacyl)-sulfonamido-5’-deoxyadenosine Precursor:
• adenosine
Reactions types: Mitsunobu condensation reactions or coupling and conjugation.
Essay:
E. coli, S. Lutea and C. Albicans.
In vitro aminoacylation experiments.
Bacteria, fungi and
Aminoacyl tRNA synthetases (aaRS) in vitro
[67]
• Sulfamide adenosine derivatives (pGlu-SA) Precursor:
• Adenosine.
• 5'-amino-5'-deoxyadenosine
L-pyroglutamic acid
Reactions types: Conjugation and coupling.
Essay:Cancer cells
Aminoacyl tRNA synthetases
(aaRS)
[70]
• 8-brominated adenosine derivatives
• 8-aminated adenosine derivatives
Precursor:
• Isopropylidene-protected-adenosine
Reactions types: Oxidation and amide-coupling
Essay: Inhibitory activity against E. coli and P. Falciporum IspE.
IspE enzyme [72]
• Truncated N6-substituted 4’-oxoadenosine
• Truncated N6-substituted 4’-thioadenosine
Precursor:
• 2,3-O-isopropylidene-D-erythronic-γ-lactone.
Reactions types: lithiation-mediated stannyl transfer and palladium-catalyzed cross coupling reactions.
Essay:
• Chinese hamster ovary (CHO) cells (A1 or A3R)
• Human embryonic kidney (HEK-293) cells (A2AAR).
A3 and A2A receptors [73]
• 7-deaza-cyclic adenosine-5’-diphosphate carbocyclic ribose.
• 7-deaza-7-bromo-cyclic adenosine-5’-diphosphate carbocyclic ribose.
Precursor:
• 2,3-disubstituted pyrrole nucleoside
• Carbocyclic ribosyl amine
• Imidazole nucleoside
Reactions types: Ag+ promoted intramolecular condesation and coupling reaction.
Essay: Hemicentrotus pulcherrimus sea urchin egg homogenate.
Sea urchin egg homogenate system [77]
• (N)-Methanocarba-5′-ester adenosine derivatives Precursor:
• (N)-methanocarba adenosine
Reactions types: oxidation, substitution nucleophilic aromatic and coupling.
Essay: Dopamine transporter (DAT)
A3R and DAT [79]

(*) Solvent = H2O or MeOH.

(Source: Prepared by the author).