Protecting Groups in Oligonucleotide Synthesis

Sonveaux, Etienne

doi:10.1007/978-1-59259-513-6_1

Cited by 16 publications

(14 citation statements)

References 415 publications

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“…1-Methyladenosine itself can be easily prepared on the preparative scale by methylation of adenosine (17). Before exploring the protecting group strategy, we examined the stability of 1 under different conditions of deblocking of acyl groups which are used in oligonucleotide synthesis (18,19). In 25% aqueous ammonia, the half-time of Dimroth rearrangement of 1 to give 4 was 36 h at room temperature.…”

Section: Synthesis Of Protected 1-methyladenosinementioning

confidence: 99%

Chemical incorporation of 1-methyladenosine into oligonucleotides

Mikhailov

Rozenski

Efimtseva

et al. 2002

Nucleic Acids Research

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Section: Synthesis Of Protected 1-methyladenosinementioning

confidence: 99%

Chemical incorporation of 1-methyladenosine into oligonucleotides

Mikhailov

Rozenski

Efimtseva

et al. 2002

Nucleic Acids Research

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“…This is due to the much higher basicity of compound 3. 26,27 With respect to the other compounds, ionic species corresponding to the protecting groups (Tr, DMTr) are always formed, but their relative abundances are small (<50%) compared with the [M C Li] C peak. Some other ions, such as different adducts of the hydrolysis products and [M C LiCl C Li] C , can also be detected with low abundances in the ESI spectra.…”

Section: Resultsmentioning

confidence: 98%

Electrospray mass spectrometry of phosphoramidites, a group of acid-labile compounds

et al. 1999

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“…A more base-stable cytosine-protecting group was therefore desirable. Several new protecting groups for cytosine have been proposed in recent years [34], mostly to obtain a protecting group more labile to base -benzoyl group. For the synthesis of SNAs, a less-labile protecting group was needed.…”

Section: H-noe Experimentsmentioning

confidence: 99%

A Direct Synthesis of Nucleoside Analogs Homologated at the 3′‐ and 5′‐Positions

Schmidt

Eschgfäller

Benner

2003

Helvetica Chimica Acta

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A new route is presented to prepare analogs of nucleosides homologated at the 3'-and 5'-positions. This route, applicable to both the d-and l-enantiomeric forms, is suitable for the preparation of monomeric bishomonucleosides needed for the synthesis of oligonucleotide analogs. It begins with the known monobenzyl ether 3 of pent-2-yne-1,5-diol, which is reduced to alkenol 4. Sharpless asymmetric epoxidation of 4, followed by opening of the epoxide 5 with allylmagnesium bromide, gives a mixture of diols 6 and 7. Protection of the primary alcohol as a silyl ether followed by treatment with OsO 4 , NaIO 4 , and mild acid in MeOH, followed by reduction, yields (2R,3R) {{[(tert-butyl)diphenylsilyl]oxy}methyl}tetrahydro-2-(2-hydroxyethyl)-5-methoxyfuran ( methyl 3-{{[(tert-butyl)diphenylsilyl]oxy}methyl}-2,3,5-trideoxy-a/b-d-erythro-hexafuranoside; 10) (Scheme 1). Protected nucleobases are added to this skeleton with the aid of trimethylsilyl triflate (Scheme 2). The o-toluoyl (2-MeC 6 H 4 CO) and p-anisoyl (4-MeOC 6 H 4 CO) groups were used to protect the exocyclic amino group of cytosine. The bis-homonucleoside analogs 11 and 14a are then converted to monothiol derivatives suitable for coupling (Schemes 3 and 4) to oligonucleotide analogs with bridging S-atoms. This synthesis replaces a much longer synthesis for analogous nucleoside analogs that begins with diacetoneglucose ( 1,2 : 5,6-di-Oisopropylideneglucose), with the stereogenic centers in the final products derived from the Sharpless asymmetric epoxidation. The new route is useful for large-scale synthesis of these building blocks for the synthesis of oligonucleotide analogs.

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Protecting Groups in Oligonucleotide Synthesis

Cited by 16 publications

References 415 publications

Chemical incorporation of 1-methyladenosine into oligonucleotides

Chemical incorporation of 1-methyladenosine into oligonucleotides

Electrospray mass spectrometry of phosphoramidites, a group of acid-labile compounds

A Direct Synthesis of Nucleoside Analogs Homologated at the 3′‐ and 5′‐Positions

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