Reactions of relevance to the chemistry of aminoglycoside antibiotics. Part 7. Conversion of thiocarbonates into deoxy-sugars

Barton, Derek H. R.; Subramanian, R. K.

doi:10.1039/p19770001718

Cited by 111 publications

(30 citation statements)

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“…Forma-se exclusivamente o produto C-5-desoxi 59. Esta seletividade é atribuída à maior estabilidade do radical secundário (em C 5 ) quando comparada a do radical primário (em C 6 ) (Esquema 17) 84,98,99 .…”

Section: Desoxigenações Radicalares: O Método De Barton-mccombieunclassified

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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Section: Desoxigenações Radicalares: O Método De Barton-mccombieunclassified

Estratégias para a síntese de desoxinucluosídeos

Soares¹,

Souza²,

Ferreira³

2001

Quím. Nova

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“…Barton first demonstrated that tributylstannane-mediated hydrogenolysis of a 2',3'-0-thiocarbonyl derivative of adenosine gave a mixture of 2'-(major) and 3'-deoxy products (20). Analogous reduction of dimeric derivatives of 8 followed by deprotection would produce one equivalent of 2'-deoxynucleoside (7) and one of the parent P-D-xylofuranosyl starting material (5).…”

Section: O W S J Robins Danuta Madej Fritz Hansske John S Wilsmentioning

confidence: 99%

Nucleic acid related compounds. 53. Synthesis and biological evaluation of 2′-deoxy-β-threo-pentofuranosyl nucleosides. "Reversion to starting alcohol" in Barton-type reductions of thionocarbonates

Robins¹,

Madej²,

Hansske³

et al. 1988

Can. J. Chem.

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CLERCQ. Can. J. Chem. 66, 1258 (1 988). Treatment of selectively 3',5'-protected P -D -~y l~f~r a n~~y l nucleosides (4) with phenyl chlorothionocarbonate and DMAP followed by hydrogenolysis of the resulting (2'-0-phenoxythiocarbonyl) phenyl thionocarbonate esters (6) with tributylstannane/AIBN, and deprotection, gave 2'-deoxy-P-D-threo-pentofuranosyl nucleosides (7). Formation of a by-product bis(nuc1eosid-2'-y1)thionocarbonate dimer (8) was detected in the uracil nucleoside reaction sequence. Its subsequent reduction provides one explanation for "reversion to starting alcohol" in Barton-type deoxygenation reactions. Only the guanine 2'-deoxynucleoside analogue (76) Chem. 66, 1258Chem. 66, (1988.La rtaction des nucltosides de P-D-xylofurannosyle prottgts stlectivement en 3',5' (4) avec du chlorothionocarbonate de phCnyle et du DMAP, suivie d'une hydrogtnolyse des esters thionocarbonates de (0-phtnoxythiocarbonyl-2') de phtnyle (6) avec le tributylstannane/AIBN et d'une dtprotection, conduit aux nuclCosides du dtsoxy-2' P-D-thre'o-pentofurannosyle (7). Dans la suite de rtactions impliquant le nucltoside d'uracile, on a dttectt la formation du dimtre du thionocarbonate de bis-(nuclCosidy1-2') (8) comme sous-produit. Sa rtduction substquente permet d'expliquer la ccrtversion vers I'alcool de dtpart~ qui est observte dans des rtactions de dtsoxygtnation du type de Barton. L'analogue dCsoxy-2' nucltoside de la guanine (7b) est le seul i prtsenter une activitt antivirale (faible) (contre le virus herpts simplex de type 1).[Traduit par la revue]Methods for the synthesis of P-D-xylofuranosyl nucleosides via base-sugar coupling (ref. 1, and references therein) and for selective 2'-deoxygenation of nucleosides (2) have been developed by us previously. We now report combination of these approaches to give 2'-deoxy-P-D-threo-pentofuranosyl nucleosides (7) and their evaluation for antiviral activity in several cell systems.In the pioneering studies of the Cambridge group, Michelson and Todd (3) reported preparation of the 02,C3'-cyclonucleoside of thymidine and its hydrolysis to give 1-(2-deoxy-P-Dthreo-pentofuranosy1)thy mine (7e) in 1955. Fox and Miller (4) and Horwitz et al. (5) later described careful characterization of this product. An analogous procedure was employed (6) for the preparation of 1-(2-deoxy-P-D-threo-pentofuranosy1)uracil ( 7 4 .Goodman and co-workers (7) first prepared 9-(2-deoxy-P-Dthreo-pentofuranosy1)adenine (7a) (and its 3'-deoxy isomer) by nucleophilic ring opening (oxirane) of 9-(2,3-anhydro-P-D1yxofuranosyl)adenine with benzylthiolate followed by desulfurization. Analogous (acid-catalyzed) ring opening with bromide followed by hydrogenolysis with tributylstannane gave alternative access to the isomeric adenine 2'-(7a) and 3'-deoxythreo nucleoside products (8). Ikehara's 8-mercaptoadenineo or the previous paper in this series, see ref. 23.'~uthor to whom inquiries may be addressed at the Department of Chemistry, Brigham Young University, Provo, Utah 84602, U.S.A. S8,C2'-cyclonucleoside desul...

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“…The structures of these compounds were established as follows. Firstly 21 was treated with thiocarbonyldiimidazole to give the thionocarbonate 23, which was then reduced with tri-n-butyltin hydride according to the BartonSubramanian procedure (28) to give 22a. The latter was hydrogenated over palladium in the presence of formic acid, and the resulting trio1 22b was acetylated directly to give triacetate 22c.…”

Section: Synthetic Studiesmentioning

confidence: 99%

Chiral building blocks for amphotericin B

Liang¹,

Pauls²,

Fraser‐Reid³

et al. 1986

Can. J. Chem.

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A general plan is outlined for disconnection of the polyene macrolides, which is aimed at achieving their syntheses, as well as facilitating the determination of their absolute configurations. The plan is exemplified by amphotericin B, I, the only family member of known absolute configuration. The major chiral component is a 20-carbon chain, 111, which upon further retrosynthetic disconnection leads to three subunits, two of which correspond to the dideoxy hexoses IV and V. Although these are formally mirror images, they are best represented as the 3,4-dideoxyhexopyranoside, 1, and the 3,5-dideoxyfuranose, 2. Syntheses of 1 and 2 from readily available starting materials are described. On presente un plan gkneral de dkmembrement des macrolides poly6niques qui a pour but d'en rkaliser la synthkse ainsi que de faciliter la determination de leurs configurations absolues. Utilisant comme exemple I'amphotCricine B, le seul membre de la famille dont la configuration soit connue, on dtmontre comment le plan peut &tre opBrationalisk. Le composant chiral principal est une chaine a 20 atomes de carbone, 111, qui conduit a trois sous-unites par un dkmembrement rktrosynthetique; deux de ces sous-unites correspondent aux dideoxy hexoses IV and V. M&me si ces sous-unites sont forrnellement des images mirroirs, leurs meilleures representations sont le dideoxy-3,4 hexopyrannoside 1 et le dikoxy-3,s furannose 2. On dkcrit les syntheses des composCs 1 et 2 2 partir de produits de depart facilement accessibles.

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Reactions of relevance to the chemistry of aminoglycoside antibiotics. Part 7. Conversion of thiocarbonates into deoxy-sugars

Cited by 111 publications

References 0 publications

Estratégias para a síntese de desoxinucluosídeos

Estratégias para a síntese de desoxinucluosídeos

Nucleic acid related compounds. 53. Synthesis and biological evaluation of 2′-deoxy-β-threo-pentofuranosyl nucleosides. "Reversion to starting alcohol" in Barton-type reductions of thionocarbonates

Chiral building blocks for amphotericin B

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