General synthesis of carbanucleosides via regiospecific epoxide opening by the aglycone

Baumgartner, H.; Marschner, Christoph; Pucher, Rainer; Griengl, Herfried

doi:10.1016/s0040-4039(00)74840-4

Cited by 28 publications

(4 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For the β-DL-xylo configuration, the authors, owing to problems in the regiochemistry of the trans-hydroxylation and side-chain degradation, used the procedure employed previously in the synthesis of carbocyclic nucleosides (Scheme 6b). 161 Compound (()-171 was converted into acid (()-174. Curtius degradation gave amine (()-175, which was stereoselectively transformed into the epoxide (()-176.…”

Section: Synthesis From Non-carbohydrate Precursorsmentioning

confidence: 99%

“…4a-Carba-α- d -xylofuranose ( 173 ) was obtained from compound 172 , as mentioned above (Scheme a). For the β- dl -xylo configuration, the authors, owing to problems in the regiochemistry of the trans -hydroxylation and side-chain degradation, used the procedure employed previously in the synthesis of carbocyclic nucleosides (Scheme b) . Compound (±)- 171 was converted into acid (±)- 174 .…”

Section: 1 Synthesis Of Carbafuranoses611 Synthesis From Non-carbohyd...mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis and Conformational and Biological Aspects of Carbasugars

et al. 2007

View full text Add to dashboard Cite

Section: Synthesis From Non-carbohydrate Precursorsmentioning

confidence: 99%

Section: 1 Synthesis Of Carbafuranoses611 Synthesis From Non-carbohyd...mentioning

confidence: 99%

Synthesis and Conformational and Biological Aspects of Carbasugars

et al. 2007

View full text Add to dashboard Cite

“…Thus, they found that CCL 108 The same strategy was applied to the synthesis of carbanucleosides derived from thymine (248) and from adenine (249). 109 Also, starting from the acetate of (+)-244, derivative (-)-250 was synthesized in a six-step sequence. 110 Ohno and co-workers 111 reported an efficient synthesis of the carbocyclic nucleosides (-)-aristeromycin [(-)-123] and (-)-neplanocin A [(-)-121] (Scheme 60).…”

Section: Five-member Ringmentioning

confidence: 99%

Biocatalytic Selective Modifications of Conventional Nucleosides, Carbocyclic Nucleosides, and C-Nucleosides

2000

View full text Add to dashboard Cite

“…Accordingly, commercially available ( R )-(+)- and ( S )-(−)-glycidol were tritylated to 1 following a standard protocol and successfully ring opened with the unprotected nucleobases thymine and adenine in the presence of substoichiometric amounts of NaH, yielding 2 and 3 , respectively (Figure ) . The thymine derivative was directly transformed into the final phosphoramidite 4 , whereas the adenine derivative was first benzoylated at the exocyclic amino group, followed by the formation of the final phosphoramidite 5 for the automated solid-phase oligonucleotide synthesis.…”

mentioning

confidence: 99%

A Simple Glycol Nucleic Acid

2005

View full text Add to dashboard Cite

We here wish to disclose a novel nucleic acid analogue which displays exceptional structural simplicity and atom economy while supporting stable duplex formation. The discovered glycol nucleic acid (GNA) uses the canonical Watson-Crick base pairing scheme combined with an acyclic three-carbon propylene glycol phosphodiester backbone (Figure 1).Groundbreaking studies of the Eschenmoser group on the chemical etiology of nucleic acid structure have demonstrated that Watson-Crick base pairing can be supported by sugars in the backbone that differ from RNA or DNA. 1-3 Most surprisingly, a nucleic acid derived from a tetrose sugar (TNA) was found to be capable of antiparallel duplex formation and crosspairing with DNA and RNA (Figure 1). 4 Our laboratory is interested in structurally simplified nucleic acid backbones in order to improve synthetic accessibility of artificial duplexes. Inspired by Eschenmoser's TNA structure, we envisioned that acyclic glycol nucleosides could be synthesized just by regioselective and stereospecific nucleophilic ring opening of a "spring-loaded" epoxide. 5,6 Accordingly, commercially available (R)-(+)-and (S)-(-)-glycidol were tritylated to 1 following a standard protocol and successfully ring opened with the unprotected nucleobases thymine and adenine in the presence of substoichiometric amounts of NaH, yielding 2 and 3, respectively ( Figure 2). 7 The thymine derivative was directly transformed into the final phosphoramidite 4, whereas the adenine derivative was first benzoylated at the exocyclic amino group, followed by the formation of the final phosphoramidite 5 for the automated solid-phase oligonucleotide synthesis. With 4 and 5 in hand, we synthesized seven 18mer oligonucleotides consisting entirely out of either enantiomer of the acyclic glycol nucleotides (Table 1) (Figure 1). . (R)-(+)-glycidol yields (S)-GNA, and (S)-(-)-glycidol yields (R)-GNAFirst, we investigated duplex formation of GNA with temperature-dependent UV spectroscopy at 260 nm. Figure 3 displays the results with (S)-GNA. Mixtures (1:1) of two complementary strands, 6:7 and 8:9, yield characteristic sigmoidal melting curves with melting points (T M ) of 63°C each, thus indicating cooperative melting of GNA duplexes. No sigmoidal melting and weaker hyperchromicities were observed with the single strands alone (Figure 3a,b) or with two strands 8:10 that are complementary in a parallel fashion (Figure 3c), indicating the requirement for antiparallel duplex formation of GNA. To reassure that the duplex relies on proper Watson-Crick base pairing, we also investigated the UV melting behavior of an 18mer duplex 8:11 which contains one T:T mismatch. The stability of this duplex decreases significantly, yielding a T M of only 55°C for the single mismatched duplex. Furthermore, a duplex 8:12 with two mismatches (one T:T and one A:A) is further destabilized with a T M of only 44°C ( Figure 3c). Identical results were obtained with the enantiomeric (R)-GNA strands.For subsequent analysis, we investigated duplex forma...

show abstract

General synthesis of carbanucleosides via regiospecific epoxide opening by the aglycone

Cited by 28 publications

References 19 publications

Synthesis and Conformational and Biological Aspects of Carbasugars

Synthesis and Conformational and Biological Aspects of Carbasugars

Biocatalytic Selective Modifications of Conventional Nucleosides, Carbocyclic Nucleosides, and C-Nucleosides

A Simple Glycol Nucleic Acid

Contact Info

Product

Resources

About