Nucleic acid related compounds. 23. Transformation of ribonucleoside 2',3'-O-ortho esters into unsaturated and deoxy sugar nucleosides via enol ester-substituted iodo intermediates

Robins, Morris J.; Jones, R. A. C.; Mengel, Rudolf

doi:10.1021/ja00441a054

Cited by 40 publications

(16 citation statements)

References 5 publications

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“…Mass and l H nmr spectra of all tubercidin compounds described in this study are closely analogous to their adenosine counterparts (9,12). The mass spectra can generally be inferred from those of the adenosine analogs with all heterocyclic base-containing fragments occurring at one atomic mass unit lower in this series (14N Z'S.…”

Section: Morris J Robins Roger a Jones Et Rudolf Mengel Can J Cmentioning

confidence: 61%

“…Treatment of 3c in refluxing pyridine or with 1,5-diazabicyclo-[4.3.0]non-5-ene (DBN) in pyridine at ambient temperature gave a mixture of 5a and the furan derivative 1Oa. Selective elimination of hydrogen iodide from 3c was effected smoothly using silver acetate (12) to give 5a quantitatively. Deblocking of 5a gave crystalline 4-amino-7-(3-deoxy-bglycero -pent -3 -enofuranosyl)pyrrolo[2,3, -dlpyrimidine (5b).…”

Section: Morris J Robins Roger a Jones Et Rudolf Mengel Can J Cmentioning

confidence: 99%

“…removal of the DMPP group using potassium permanganate in cold aqueous pyridine (12 undergoes intramolecular degradation especially in hydroxylic solvents. By analogy with the adenosine ribo-epoxide (15), it is assumed that nucleophilic attack by N-1 at C-3' of the epoxide gives transitory N1-+3'-cyclonucleoside formation.…”

Section: Morris J Robins Roger a Jones Et Rudolf Mengel Can J Cmentioning

confidence: 99%

“…The pertinent literature and new procedures for deoxy and unsaturated compounds are described in ref. 12.…”

Section: Morris J Robins Roger a Jones Et Rudolf Mengel Can J Cmentioning

confidence: 99%

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Nucleic acid related compounds. 24. Transformation of tubercidin 2′,3′-O-orthoacetate into halo, deoxy, epoxide, and unsaturated sugar nucleosides

Robins¹,

Jones²,

Mengel³

1977

Can. J. Chem.

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Treatment of tubercidin (4-amino-7-β-D-ribofuranosylpyrrolo[2,3-d]pyrimidine) (1) with methyl orthoacetate gave the 2′,3′-O-orthoester, 2. Pivalic acid chloride in refluxing pyridine converted 2 into a mixture containing 4-N-pivalamido-7-(3-chloro-3-deoxy-2-O-acetyl-5-O-pivalyl-β-D-xylofuranosyl)pyrrolo[2,3-d)pyrimidine (3a) and the corresponding 2′-O-(4,4-dimethyl-3-pivaloxypent-2-enoyl) (DMPP) compound (3b) via acetoxonium ion intermediates. Treatment of 2 with sodium iodide/pivalyl chloride/pyridine gave the iodo analog (3c) of DMPP derivative 3b plus the 3′,4′-unsaturated nucleoside (5a). Treatment of 3a–c with methanolic sodium methoxide gave the ribo-epoxide 4, which underwent N1 → 3′ intramolecular cyclization readily. Dehalogenation of 3 and deprotection gave 3′-deoxytubercidin (8). Deblocking of 5a gave 5b which was hydrogenated to give 8 plus its 4′-epimer 9. Heating of 3c or 5a produced 4-N-pivalamido-7-(5-pivaloxymethylfuran-2-yl)pyrrolo[2,3-d]pyrimidine (10a). Deblocking of 10a gave 10d which was hydrogenated to give racemic 4-amino-7-(2,3-dideoxy-β-D,L-glycero-pentofuranosyl)pyrrolo[2,3-d]pyrimidine (7,11). The 2′,3′-unsaturated nucleoside (6) was obtained and hydrogenated to produce 2′,3′-dideoxytubercidin (7). Spectroscopic identification of products, epoxide instability, and comparison with other procedures are discussed.

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Section: Morris J Robins Roger a Jones Et Rudolf Mengel Can J Cmentioning

confidence: 61%

Section: Morris J Robins Roger a Jones Et Rudolf Mengel Can J Cmentioning

confidence: 99%

Section: Morris J Robins Roger a Jones Et Rudolf Mengel Can J Cmentioning

confidence: 99%

“…The pertinent literature and new procedures for deoxy and unsaturated compounds are described in ref. 12.…”

Section: Morris J Robins Roger a Jones Et Rudolf Mengel Can J Cmentioning

confidence: 99%

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Nucleic acid related compounds. 24. Transformation of tubercidin 2′,3′-O-orthoacetate into halo, deoxy, epoxide, and unsaturated sugar nucleosides

Robins¹,

Jones²,

Mengel³

1977

Can. J. Chem.

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“…Esta metodologia previne a formação do subproduto 2',5'-dibromado, observado quando se usa a reação de Mansuri. Na realidade, esta metodologia de metoxietilidenação já havia sido empregada por Robins e colaboradores, sendo pouco explorada pelos autores [55][56][57] . Trans-iodoacetatos foram também preparados usando-se uma mistura de cloreto de 2-acetoxi-isobutirila e iodeto de sódio 58 .…”

Section: Métodos De Desoxigenação Com Derivatização Préviaunclassified

Estratégias para a síntese de desoxinucluosídeos

Soares¹,

Souza²,

Ferreira³

2001

Quím. Nova

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Recebido em 18/2/00; aceito em 16/8/00 STRATEGIES FOR THE SYNTHESES OF DEOXINUCLEOSIDES. The number of agents available for the treatment of viral infections has increased dramatically during the past decade most of them belonging to the nucleoside class. The accomplishment of many syntheses for these nucleosides in recent years offers evidence that the field is very important for the organic synthesis. The discussion of several approaches for preparing deoxy and dehydronucleosides is reviewed in a simplified way.

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Mechanism of Diol Dehydration by a Promiscuous Radical‐SAM Enzyme Homologue of the Antiviral Enzyme Viperin (RSAD2)

et al. 2020

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has made ap rovisionalp atent application based on the discoveries demonstrated in this manuscript.Keywords: antiviral agents · nucleotide analogues · radical-SAM enzyme · tyrosyl radicals · viperin Figure 6. The proposed mechanism of catalysis by TtRSAD2. The 5'-dAdo radicalabstractst he Ha tom (red) at the C4' position of ribose to generate a C4'-centred radical intermediate. As ar esult of hyperconjugation between a po rbitalonC 4' and the s C3'ÀO3' orbital, assisted by ap rotein amino acid residue( AH), the 3'-OHg roupo ft he riboseforms awater molecule. The proton to generate the water molecule is provided by tyrosine either indirectly through ap roton hoppingp athway(1) or directly (2). Spontaneously, an electron from tyrosine reduces the substrate-radical intermediate. As a result, the nucleotide analogue product and ap rotein tyrosylradical are formed. The [4 FeÀ4S] 2 + clusteri sre-reduced and then,t he tyrosyl radicali s reducedbya ne lectron from the [4 FeÀ4S] + cluster.

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Nucleic acid related compounds. 23. Transformation of ribonucleoside 2',3'-O-ortho esters into unsaturated and deoxy sugar nucleosides via enol ester-substituted iodo intermediates

Cited by 40 publications

References 5 publications

Nucleic acid related compounds. 24. Transformation of tubercidin 2′,3′-O-orthoacetate into halo, deoxy, epoxide, and unsaturated sugar nucleosides

Nucleic acid related compounds. 24. Transformation of tubercidin 2′,3′-O-orthoacetate into halo, deoxy, epoxide, and unsaturated sugar nucleosides

Estratégias para a síntese de desoxinucluosídeos

Mechanism of Diol Dehydration by a Promiscuous Radical‐SAM Enzyme Homologue of the Antiviral Enzyme Viperin (RSAD2)

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