Formation of an Unexpected 2-Deoxy-α-D-Threo-Pentofuranosyl Azide by Reaction of O<sup>2</sup>,3′-Anhydro-5′-O-trityl-2′-deoxycytidine with Lithium Azide

Mikhailopulo, Igor A.; Зайцева, Г. С.; Vaaks, E. V.; Rosemeyer, H.; Seela, Frank

doi:10.1080/07328319208021702

Cited by 6 publications

(5 citation statements)

References 5 publications

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“…(1) with diethylaminosulfur trifluoride (DAST) or morpholinosulfur trifluoride (MSTF) in anhydrous dioxane at room temperature [14,151 afforded the 2,2'-anhydro nucleoside 2. Benzoylation of the latter gave the benzoate 3.…”

Section: Treatment Of 1-(5-o-trityl-~-~-ribof~ranosyl)thymine[~~]mentioning

confidence: 99%

Synthesis of 2′‐Azido‐2′,3′‐didehydro‐2′,3′‐dideoxythymidine

et al. 1993

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Compound 15 – the 2′‐azido analog of the anti‐HIV compound 2′,3′‐didehydro‐2′,3′‐dideoxythymidine – was synthesized. Treatment of 5′‐O‐trityl‐β‐D‐ribofuranosylthymine (1) with DAST or MSTF gave the 2,2′‐anhydro derivative 2. The latter and its 3′‐O‐benzoate 3 were used for the synthesis of the 2′‐azido‐2′‐deoxy derivatives 4 and 5. Two routes to the synthesis of 15 from 5 were investigated. (i) Treatment of 5 with DAST gave a mixture of the 5′‐O‐trityl derivatives 12 and 13 as well as 1‐(2‐azido‐2,3‐dideoxy‐3‐fluoro‐β‐D‐xylofuranosyl)thymine (16) along with 2,3′‐anhydro derivative 14 (2%). Detritylation of the mixture yielded 15 (39%) and 16 (12%). (ii) Mesylation of 5 gave 17 which yielded 15 upon saponification and detritylation. Compound 15 showed moderate inhibitory activity against HIV‐1 and HIV‐2 in MT‐4 cells.

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Section: Treatment Of 1-(5-o-trityl-~-~-ribof~ranosyl)thymine[~~]mentioning

confidence: 99%

Synthesis of 2′‐Azido‐2′,3′‐didehydro‐2′,3′‐dideoxythymidine

et al. 1993

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“…With this protecting group, anhydronucleoside 16 could be readily separated from triphenylphosphine oxide and other contaminations through precipitation from diethylether. Interestingly, the addition of lithium chloride to the reaction mixture of the ring opening to compound 17 26 lowered the yield by favoring opening at the anomeric position with concomitant loss of benzoylcytosine.…”

Section: Resultsmentioning

confidence: 99%

Convenient Syntheses of 3′-Amino-2′,3′-dideoxynucleosides, Their 5′-Monophosphates, and 3′-Aminoterminal Oligodeoxynucleotide Primers

Eisenhuth

Richert

2008

J. Org. Chem.

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5'-Protected 3'-amino-2',3'-dideoxynucleosides containing any of the four canonical nucleobases (A/C/G/T) were prepared via azides in five to six steps, starting from deoxynucleosides. For pyrimidines, the synthetic route involved nucleophilic opening of anhydronucleosides. For purines, an in situ oxidation/reduction sequence, followed by a Mitsunobu reaction with diphenyl-2-pyridylphosphine and sodium azide, provided the 3'-azidonucleosides in high yield and purity. For solid-phase synthesis of aminoterminal oligonucleotides, aminonucleosides were linked to controlled pore glass through a novel hexafluoroglutaric acid linker. These supports gave 3'-aminoterminal primers in high yield and purity via conventional DNA chain assembly and one-step deprotection/release with aqueous ammonia. Primers thus prepared were successfully tested in enzyme-free chemical primer extension, an inexpensive methodology for genotyping and labeling. Protected 5'-monophosphates of 3'-amino-2',3'-dideoxynucleosides were also prepared, providing starting materials for the preparation of labeled or photolably protected monomers for chemical primer extension.

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“…The synthesis of the 2‘-deoxycytidine (“C”) monomer is shown in Scheme . Compound 2c was found to be more readily and efficiently synthesized employing the dU → dC route depicted in Scheme , rather than via lithium azide ring-opening of the 2,3‘-anhydro-2‘-deoxycytidine derivative . Selective silylation of the 5‘-OH of 2‘-deoxyuridine with tert -butyldimethylsilyl chloride, Mitsonobu reaction facilitated ring-closure, and subsequent ring-opening with lithium azide afforded a 63% yield of 1du .…”

Section: Resultsmentioning

confidence: 99%

N3‘→P5‘ Oligodeoxyribonucleotide Phosphoramidates: A New Method of Synthesis Based on a Phosphoramidite Amine-Exchange Reaction

et al. 1997

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A new method for the synthesis of N3'-->P5' phosphoramidate oligodeoxynucleotides is demonstrated. Described herein is the synthesis of the monomers utilized in the phosphoramidite amine-exchange process and the experimental details pertaining to this new mode of chain assembly. The phosphoramidite amine-exchange method generates coupling yields in the 92-95% range per cycle and further enables the synthesis of chimeric phosphoramidate/phosphodiester or phosphoramidate/phosphorothioate oligonucleotides with no instrument modifications.

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Formation of an Unexpected 2-Deoxy-α-D-Threo-Pentofuranosyl Azide by Reaction of O²,3′-Anhydro-5′-O-trityl-2′-deoxycytidine with Lithium Azide

Cited by 6 publications

References 5 publications

Synthesis of 2′‐Azido‐2′,3′‐didehydro‐2′,3′‐dideoxythymidine

Synthesis of 2′‐Azido‐2′,3′‐didehydro‐2′,3′‐dideoxythymidine

Convenient Syntheses of 3′-Amino-2′,3′-dideoxynucleosides, Their 5′-Monophosphates, and 3′-Aminoterminal Oligodeoxynucleotide Primers

N3‘→P5‘ Oligodeoxyribonucleotide Phosphoramidates: A New Method of Synthesis Based on a Phosphoramidite Amine-Exchange Reaction

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Formation of an Unexpected 2-Deoxy-α-D-Threo-Pentofuranosyl Azide by Reaction of O2,3′-Anhydro-5′-O-trityl-2′-deoxycytidine with Lithium Azide

Cited by 6 publications

References 5 publications

Synthesis of 2′‐Azido‐2′,3′‐didehydro‐2′,3′‐dideoxythymidine

Synthesis of 2′‐Azido‐2′,3′‐didehydro‐2′,3′‐dideoxythymidine

Convenient Syntheses of 3′-Amino-2′,3′-dideoxynucleosides, Their 5′-Monophosphates, and 3′-Aminoterminal Oligodeoxynucleotide Primers

N3‘→P5‘ Oligodeoxyribonucleotide Phosphoramidates: A New Method of Synthesis Based on a Phosphoramidite Amine-Exchange Reaction

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Formation of an Unexpected 2-Deoxy-α-D-Threo-Pentofuranosyl Azide by Reaction of O²,3′-Anhydro-5′-O-trityl-2′-deoxycytidine with Lithium Azide