Halo sugar nucleosides. I. Iodination of the primary hydroxyl groups of nucleosides with methyltriphenoxyphosphonium iodide

Verheyden, Julien P. H.; Moffatt, J. G.

doi:10.1021/jo00832a047

Cited by 160 publications

(81 citation statements)

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“…This product was not characterized but used without further purification for decarboxylation. Methyl I-(P-~Ribofuranosy1)-v-triazole-4-carboxylate (25) The tri-0-benzoyl derivative 24a (493.8 mg, 0.864 mmol) was deblocked with sodium methoxide and methanol using the same procedure as used for the preparation of 26. The crude product weighed 200 mg (89%) and had a mp of 147-150°C.…”

Section: Methyl 5-formyl-l-(235-tri-o-benzoyl-~-~-ribofuranosyl)-v-mentioning

confidence: 99%

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The synthesis of 8-aza-3-deazaguanosine [6-amino-1-(β-D-ribofuranosyl)-υ-triazolo[4,5-c]pyridin-4-one] via a novel 1,3-dipolar cycloaddition reaction

Earl¹,

Townsend²

1980

Can. J. Chem.

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8-Aza-3-deazaguanosine (2) bas been prepared via a route which used a 1,3-dipolar cycloaddition reaction to provide a key intermediate. The reaction of 2′,3′,5′-tri-O-benzoyl-β-D-ribofuranosyl azide (13) with methyl 4-hydroxy-2-butynoate (11) provided a good yield of crystalline methyl 5-hydroxymethyl-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-υ-triazole-4-carboxylate (14). A series of functional group transformations were then used to convert 14 into methyl 5-cyanomethyl-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-υ-triazolo-4-carboxylate (19). Treatment of 19 with liquid ammonia effected not only a smooth removal of the blocking groups, but also an aminolysis of the ester function which was then followed by a ring annulation to provide 8-aza-3-deazaguanosine (2). The structures of these nucleosides were established on the basis of proton nmr spectral data and nuclear Overhauser enhancement data. The nucleosides obtained in this study were also converted through a chemical degradation sequence into nucleosides which had been obtained during an earlier work from our laboratory. The present study also provides unequivocal proof of the structures of some triazole nucleosides obtained in the earlier study.

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Section: Methyl 5-formyl-l-(235-tri-o-benzoyl-~-~-ribofuranosyl)-v-mentioning

confidence: 99%

“…certain acetylenic alcohols under very mild conditions. Other methods for bromination (24) and iodination (25) were also unsuccessful in converting 11 into a halo derivative. Similarly, methods (26) for the preparation of mesylates and tosylates from acetylenic alcohols did not give useful products from 11.…”

mentioning

confidence: 99%

The synthesis of 8-aza-3-deazaguanosine [6-amino-1-(β-D-ribofuranosyl)-υ-triazolo[4,5-c]pyridin-4-one] via a novel 1,3-dipolar cycloaddition reaction

Earl¹,

Townsend²

1980

Can. J. Chem.

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“…Further treatment of 13 with methyltriphenoxyphosphonium iodide 13 to obtain the corresponding iodide (as precursor for phosphonylation) afforded exclusively the hitherto-unknown tricycle 15 (a 5-thia-1, 2-diaza-cyclopenta[cd]pentalene system) as a viscous oil. With chloride 14 under Arbuzov conditions no phosphonate was observed but it again gave 15.…”

Section: Side-chain Transformations 1 (Fig 4)mentioning

confidence: 99%

Synthesis of a biotin-like phosphonate model compound for (+)-hydantocidin

Föry

Tobler

1999

Pestic. Sci.

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Approaches to the synthesis of a biotinlike phosphonate are described. It was hoped that this would be a simpler model compound for the * Correspondence to: Hans Tobler, Novartis Crop Protection AG, Business Unit Herbicides, R-1047.110, CH-4002 Basel, Switzerland E-mail: hans.tobler@cp.novartis.com (Received 1 July 1998; revised version 20 August 1998; accepted 16 February 1999) 668Pestic Sci 55:633±675 (1999)Extended Summaries: IUPAC Congress naturally occurring spironucleoside ()-hydantocidin, but it showed no activity as a herbicide nor as an inhibitor of AdSS.Keywords: ()-hydantocidin; model compound; phosphonate; biotin-like 1 INTRODUCTION ()-Hydantocydin (1a; Fig 1) is a naturally occurring spironucleoside with potent herbicidal activity and is produced by certain strains of the actinomycete Streptomyces hygroscopicus (Tu È 2474). 1 It is actually a pro-herbicide, in that the corresponding 5'-phosphate (1b) inhibits adenylosuccinate synthetase (AdSS) in de-novo purine biosynthesis. 1,2The presently known synthetic methods for the parent compound 1a are not economically feasible and its close analogues lack biological activity.1 Since X-ray data of the enzyme-inhibitor complex 1b became available, the search for AdSS inhibitors has focused upon the CAMM-supported design of simpler model compounds: as an example, the biotin-like phosphonate 2 ful®ls the steric requirements for an AdSS inhibitor.Racemic 2 was synthesised in seven steps from the phosphonium salt 3a (Fig 2), a close analogue of a recently identi®ed biotin process key intermediate, 3 by using Wittig methodology for the introduction of the side chain (5) followed by appropriate functional group transformations and deprotection. In view of the well-known vigorous N-debenzylation reactions in biotin chemistry, a parallel synthesis using paramethoxybenzyl as a more-easily cleaved N-protecting group was carried out using 3b as starting material. The choice of protecting group proved to be critical. The key intermediates 3 are readily produced in two steps from thiolactones 4. 3±7 SYNTHESES 2.1 Introduction of side chain (Fig 3)Wittig reaction of phosphoranes derived from rac-3 with TBDMS-protected 2-hydroxy acetaldehyde 8,9 competed with reductive formation of thiophanes 6 and 7. The choice of base was crucial. Best results on a preparative scale (20 mmol) were achieved in the benzyl series with solid KN(TMS) 2 in the presence of a catalytic amount of 18-crown-6, 10 thus affording the exocyclic allylic silyl ether 5a in 66% yield (E-con®guration predominant), accompanied by the thiophane 6a.11 On the other hand, an analogous Wittig reaction with 3b under similar conditions proceeded disappointingly, 6b and 7b becoming the major components due to migration of the neighbouring p-MeO-phenyl moiety into the 2a-position. Thus Pestic Sci 55:633±675 (1999) 669Extended Summaries: IUPAC Congress the p-Meo-benzyl series was abandoned. Treatment of 3a with base alone furnished 6a as the sole product. Side-chain transformations 1 (Fig 4)Catalytic...

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“…It can be expected that the requested final produ-t, lycoricidine triacetate (19), will become available within the next three months.…”

Section: Avs Ribmentioning

confidence: 99%

Chemical Preparation Laboratory for IND Candidate Compounds

Schubert¹

1989

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Halo sugar nucleosides. I. Iodination of the primary hydroxyl groups of nucleosides with methyltriphenoxyphosphonium iodide

Cited by 160 publications

References 4 publications

The synthesis of 8-aza-3-deazaguanosine [6-amino-1-(β-D-ribofuranosyl)-υ-triazolo[4,5-c]pyridin-4-one] via a novel 1,3-dipolar cycloaddition reaction

The synthesis of 8-aza-3-deazaguanosine [6-amino-1-(β-D-ribofuranosyl)-υ-triazolo[4,5-c]pyridin-4-one] via a novel 1,3-dipolar cycloaddition reaction

Synthesis of a biotin-like phosphonate model compound for (+)-hydantocidin

Chemical Preparation Laboratory for IND Candidate Compounds

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