Nucleic acid related compounds. 22. Transformation of ribonucleoside 2',3'-O-ortho esters into halo, deoxy, and epoxy sugar nucleosides using acyl halides. Mechanism and structure of products

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

doi:10.1021/ja00441a053

Cited by 43 publications

(33 citation statements)

References 9 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: 62%

“…DthalogCnation de 3 et diprotection donne la dCoxy-3' tubercidine (8). DCblocage de 5a donne 56 qui est hydrogene et donne 8 avec son Cpimkre-4' (9). La N-pivalamido-4 (pivaloxymethyl-5 furanyl-2)-7 pyrrolo[2,3-dlpyrimidine (IOU) est produire lors du chauffage de 3c ou §a.…”

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

“…Prior deblocking of 100 gave the hydroxymethylfuran derivative (IOd) which underwent hydrogenation of the furan ring to give racemic 4-amino-7-(2.3-dideoxy-P-D~L-glycero-pentofura~osyl)pyrrolo[2,3-dlpyrimidine (9,111. The cis orientation of the base (1') and hydroxymethyl (4') substituents of 7,Bl was verified by 5'-0-tosylation followed by quantitative ~yclization (tlc, uv) to the PT1+5'-~~clonucleo-sides (3,9,14 …”

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

confidence: 99%

“…The mechanisms of the orthoester -pivalyl halide reactions involving acyloxonium ion and ketene acetal intermediates and proofs of structures of the products are discussed in detail in ref. 9. The pertinent literature and new procedures for deoxy and unsaturated compounds are described in ref.…”

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: 62%

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

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%

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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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“…2a(Z) (viscous oil): MS (CI, CH,) m/z: 571 (100, "Diffusion crystallizationn was performed with the noted solvent MH', Iz0sn), 569 (72, MH', "'~n), 567 (43, MH', "%n). combinations as described (21). Thin-layer chromatography (TLC) was performed on Merck Kieselgel60 F, , sheets with: Sl (Me2CO/ CHCl,, 1:3), S2 (EtOAc/hexane, 7 : 3), or S3 (MeOH/CHC13, 1 :9) with sample observation under 254 nm light.…”

Section: Methodsmentioning

confidence: 99%

Nucleic acid related compounds. 78. Stereocontrolled syntheses of 6′(E and Z)-halovinyl analogues from uridine-derived vinylsulfones via vinyltin intermediates

Wnuk¹,

Robins²

1993

Can. J. Chem.

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Treatment of the 6′(E)-tosylvinyl homonucleoside 1a with Bu3SnH/AIBN/toluene/Δ gave separable mixtures of 6′-vinylstannanes 2a(E/Z) in high yields. Stereospecific halodestannylations with N-iodosuccinimide, bromine, and N-bromosuccinimide proceeded smoothly to give the 6′(E or Z)-iodo(and bromo) vinyl compounds with retention of configuration. Chlorine or iodobenzene dichloride effected moderately stereoselective chlorodestannylation. Treatment of 2a with NH4F/MeOH/Δ resulted in carbon–tin bond cleavage to give the free vinyl derivative 4a. Aqueous trifluoroacetic acid effected concomitant protiodestannylation and deprotection of 2a to give 4b. Treatment of 2a(E) with lead tetraacetate/acetonitrile and deprotection afforded acetylenic derivative 3b.

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Reduction of Ribonucleosides to 2′‐Deoxyribonucleosides

Robins

Wnuk

2005

CP Nucleic Acid Chemistry

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Ribonucleosides are converted into 2'-deoxyribonucleosides in good yields by a four-step procedure. Selective protection of the 3'- and 5'-hydroxyl groups with 1,3-dichloro-1,1,3,3-tetraisopropyl-1,3-disiloxane is followed by functionalization of the 2'-hydroxyl group with phenoxythiocarbonyl chloride. Free radical-mediated reductive C2'-O2' bond cleavage of these 3',5'-O-TPDS-2'-O-PTC-nucleoside derivatives with tributyltin hydride, followed by removal of the silyl protecting group with tetrabutylammonium fluoride, provides the 2'-deoxyribonucleosides. Adenosine, cytidine, guanosine, and uridine are converted into dA, dC, dG, and dU in overall yields of 60% to 80%. Use of tributyltin deuteride in the reductive cleavage step gives 2'-deuterio-2'-deoxyadenosine in 81% yield from adenosine with >85% retention of configuration at C2'. Application of this four-step protocol with nucleoside analogs is straightforward.

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Nucleic acid related compounds. 22. Transformation of ribonucleoside 2',3'-O-ortho esters into halo, deoxy, and epoxy sugar nucleosides using acyl halides. Mechanism and structure of products

Cited by 43 publications

References 9 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

Nucleic acid related compounds. 78. Stereocontrolled syntheses of 6′(E and Z)-halovinyl analogues from uridine-derived vinylsulfones via vinyltin intermediates

Reduction of Ribonucleosides to 2′‐Deoxyribonucleosides

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