Reaction of N3-benzoyl-3′,5′-O-(di-tertbutylsilanediyl)uridine with hindered electrophiles: Intermolecular N3 to 2′-O protecting group transfer

Lei Zhu, Osvaldo Dos Santos, Nadrian Seeman, James Canary

Research output: Contribution to journalArticle

Abstract

The compound N3-benzoyl-3′,5′-O-(di-tert-butylsilanediyl)uridine 2 was alkylated with various alkyl iodides in CH3CN in the presence of base. Normal 2′-O-alkylated products were obtained with methyl or benzyl iodide. If hindered alkyl iodides with β-branching such as 2-ethylbutyl iodide were used as electrophiles under the same conditions, N3-alkyl-2′-O-benzoyl uridine derivatives were produced. This unexpected transformation is usually dormant with reactive alkylating agents, but expressed with sterically hindered, less reactive electrophiles. This unwanted reaction gives isomeric products whose spectra differ in only subtle ways from target compounds.

Original languageEnglish (US)
Pages (from-to)723-735
Number of pages13
JournalNucleosides, Nucleotides and Nucleic Acids
Volume21
Issue number10
DOIs
StatePublished - 2002

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Uridine
Iodides
Alkylating Agents
Derivatives

Keywords

  • 2′-O-Alkyl ribonucleosides
  • Alkylation reaction
  • Protecting group

ASJC Scopus subject areas

  • Biochemistry
  • Genetics

Cite this

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title = "Reaction of N3-benzoyl-3′,5′-O-(di-tertbutylsilanediyl)uridine with hindered electrophiles: Intermolecular N3 to 2′-O protecting group transfer",
abstract = "The compound N3-benzoyl-3′,5′-O-(di-tert-butylsilanediyl)uridine 2 was alkylated with various alkyl iodides in CH3CN in the presence of base. Normal 2′-O-alkylated products were obtained with methyl or benzyl iodide. If hindered alkyl iodides with β-branching such as 2-ethylbutyl iodide were used as electrophiles under the same conditions, N3-alkyl-2′-O-benzoyl uridine derivatives were produced. This unexpected transformation is usually dormant with reactive alkylating agents, but expressed with sterically hindered, less reactive electrophiles. This unwanted reaction gives isomeric products whose spectra differ in only subtle ways from target compounds.",
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T1 - Reaction of N3-benzoyl-3′,5′-O-(di-tertbutylsilanediyl)uridine with hindered electrophiles

T2 - Intermolecular N3 to 2′-O protecting group transfer

AU - Zhu, Lei

AU - Dos Santos, Osvaldo

AU - Seeman, Nadrian

AU - Canary, James

PY - 2002

Y1 - 2002

N2 - The compound N3-benzoyl-3′,5′-O-(di-tert-butylsilanediyl)uridine 2 was alkylated with various alkyl iodides in CH3CN in the presence of base. Normal 2′-O-alkylated products were obtained with methyl or benzyl iodide. If hindered alkyl iodides with β-branching such as 2-ethylbutyl iodide were used as electrophiles under the same conditions, N3-alkyl-2′-O-benzoyl uridine derivatives were produced. This unexpected transformation is usually dormant with reactive alkylating agents, but expressed with sterically hindered, less reactive electrophiles. This unwanted reaction gives isomeric products whose spectra differ in only subtle ways from target compounds.

AB - The compound N3-benzoyl-3′,5′-O-(di-tert-butylsilanediyl)uridine 2 was alkylated with various alkyl iodides in CH3CN in the presence of base. Normal 2′-O-alkylated products were obtained with methyl or benzyl iodide. If hindered alkyl iodides with β-branching such as 2-ethylbutyl iodide were used as electrophiles under the same conditions, N3-alkyl-2′-O-benzoyl uridine derivatives were produced. This unexpected transformation is usually dormant with reactive alkylating agents, but expressed with sterically hindered, less reactive electrophiles. This unwanted reaction gives isomeric products whose spectra differ in only subtle ways from target compounds.

KW - 2′-O-Alkyl ribonucleosides

KW - Alkylation reaction

KW - Protecting group

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