O-selectivity and utility of phosphorylation mediated by phosphite triester intermediates in the N-unprotected phosphoramidite method.
Identifieur interne : 000302 ( Ncbi/Curation ); précédent : 000301; suivant : 000303O-selectivity and utility of phosphorylation mediated by phosphite triester intermediates in the N-unprotected phosphoramidite method.
Auteurs : Akihiro Ohkubo [Japon] ; Yusuke Ezawa ; Kohji Seio ; Mitsuo SekineSource :
- Journal of the American Chemical Society [ 0002-7863 ] ; 2004.
Descripteurs français
- KwdFr :
- ADN (), Composés organiques du phosphore (), Désoxyadénosine (), Désoxycytidine (), Désoxycytidine (analogues et dérivés), Modèles moléculaires, Oligodésoxyribonucléotides (), Oligodésoxyribonucléotides (synthèse chimique), Oligonucléotides (), Oligonucléotides (synthèse chimique), Phosphites (), Phosphorylation, Thermodynamique.
- MESH :
- analogues et dérivés : Désoxycytidine.
- synthèse chimique : Oligodésoxyribonucléotides, Oligonucléotides.
- ADN, Composés organiques du phosphore, Désoxyadénosine, Désoxycytidine, Modèles moléculaires, Oligodésoxyribonucléotides, Oligonucléotides, Phosphites, Phosphorylation, Thermodynamique.
English descriptors
- KwdEn :
- DNA (chemistry), Deoxyadenosines (chemistry), Deoxycytidine (analogs & derivatives), Deoxycytidine (chemistry), Models, Molecular, Oligodeoxyribonucleotides (chemical synthesis), Oligodeoxyribonucleotides (chemistry), Oligonucleotides (chemical synthesis), Oligonucleotides (chemistry), Organophosphorus Compounds (chemistry), Phosphites (chemistry), Phosphorylation, Thermodynamics.
- MESH :
- chemical , analogs & derivatives : Deoxycytidine.
- chemical , chemical synthesis : Oligodeoxyribonucleotides, Oligonucleotides.
- chemical , chemistry : DNA, Deoxyadenosines, Deoxycytidine, Oligodeoxyribonucleotides, Oligonucleotides, Organophosphorus Compounds, Phosphites.
- Models, Molecular, Phosphorylation, Thermodynamics.
Abstract
Previously, O-selective phosphorylation on polymer supports in the N-unprotected phosphoramidite method could not be carried out because the amino groups of dA and dC have high reactivity toward tervalent phosphorus(III)-type phosphitylating reagents. In this paper, we developed a new coupling strategy named the "activated phosphite method" in which the phosphitylation is mediated by phosphite triester intermediates 1. Application of 1-hydroxybenzotriazole as the promoter to the solid-phase synthesis resulted in excellent O-selectivity of more than 99.7%. This O-selectivity was explained by the frontier molecular orbital interactions between the reactive intermediates and the nucleophiles such as the amino or hydroxyl groups of nucleosides. Furthermore, longer oligonucleotides were synthesized not only by a manual operation but also by a DNA synthesizer. The utility of our new method was demonstrated by the successful synthesis of a base-labile modified oligodeoxyribonucleotide having 4-N-acetyldeoxycytidine residues. Finally, DNA 20-mers containing dA or dC could be synthesized in good yields by use of a combined reagent of 6-trifluoromethyl-1-hydroxybenzotriazole and benzimidazolium triflate.
DOI: 10.1021/ja048125h
PubMed: 15339173
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pubmed:15339173Le document en format XML
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sortKey="Ezawa, Yusuke" sort="Ezawa, Yusuke" uniqKey="Ezawa Y" first="Yusuke" last="Ezawa">Yusuke Ezawa</name></author><author><name sortKey="Seio, Kohji" sort="Seio, Kohji" uniqKey="Seio K" first="Kohji" last="Seio">Kohji Seio</name></author><author><name sortKey="Sekine, Mitsuo" sort="Sekine, Mitsuo" uniqKey="Sekine M" first="Mitsuo" last="Sekine">Mitsuo Sekine</name></author></titleStmt><publicationStmt><idno type="wicri:source">PubMed</idno><date when="2004">2004</date><idno type="RBID">pubmed:15339173</idno><idno type="pmid">15339173</idno><idno type="doi">10.1021/ja048125h</idno><idno type="wicri:Area/PubMed/Corpus">002370</idno><idno type="wicri:explorRef" wicri:stream="PubMed" wicri:step="Corpus" wicri:corpus="PubMed">002370</idno><idno type="wicri:Area/PubMed/Curation">002370</idno><idno type="wicri:explorRef" wicri:stream="PubMed" wicri:step="Curation">002370</idno><idno type="wicri:Area/PubMed/Checkpoint">002248</idno><idno type="wicri:explorRef" wicri:stream="Checkpoint" 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Midoriku, Yokohama 226-8501</wicri:regionArea><wicri:noRegion>Yokohama 226-8501</wicri:noRegion></affiliation></author><author><name sortKey="Ezawa, Yusuke" sort="Ezawa, Yusuke" uniqKey="Ezawa Y" first="Yusuke" last="Ezawa">Yusuke Ezawa</name></author><author><name sortKey="Seio, Kohji" sort="Seio, Kohji" uniqKey="Seio K" first="Kohji" last="Seio">Kohji Seio</name></author><author><name sortKey="Sekine, Mitsuo" sort="Sekine, Mitsuo" uniqKey="Sekine M" first="Mitsuo" last="Sekine">Mitsuo Sekine</name></author></analytic><series><title level="j">Journal of the American Chemical Society</title><idno type="ISSN">0002-7863</idno><imprint><date when="2004" type="published">2004</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>DNA (chemistry)</term><term>Deoxyadenosines (chemistry)</term><term>Deoxycytidine (analogs & derivatives)</term><term>Deoxycytidine (chemistry)</term><term>Models, Molecular</term><term>Oligodeoxyribonucleotides (chemical synthesis)</term><term>Oligodeoxyribonucleotides (chemistry)</term><term>Oligonucleotides (chemical synthesis)</term><term>Oligonucleotides (chemistry)</term><term>Organophosphorus Compounds (chemistry)</term><term>Phosphites (chemistry)</term><term>Phosphorylation</term><term>Thermodynamics</term></keywords><keywords scheme="KwdFr" xml:lang="fr"><term>ADN ()</term><term>Composés organiques du phosphore ()</term><term>Désoxyadénosine ()</term><term>Désoxycytidine ()</term><term>Désoxycytidine (analogues et dérivés)</term><term>Modèles moléculaires</term><term>Oligodésoxyribonucléotides ()</term><term>Oligodésoxyribonucléotides (synthèse chimique)</term><term>Oligonucléotides ()</term><term>Oligonucléotides (synthèse chimique)</term><term>Phosphites ()</term><term>Phosphorylation</term><term>Thermodynamique</term></keywords><keywords scheme="MESH" type="chemical" qualifier="analogs & derivatives" xml:lang="en"><term>Deoxycytidine</term></keywords><keywords scheme="MESH" type="chemical" qualifier="chemical synthesis" xml:lang="en"><term>Oligodeoxyribonucleotides</term><term>Oligonucleotides</term></keywords><keywords scheme="MESH" type="chemical" qualifier="chemistry" xml:lang="en"><term>DNA</term><term>Deoxyadenosines</term><term>Deoxycytidine</term><term>Oligodeoxyribonucleotides</term><term>Oligonucleotides</term><term>Organophosphorus Compounds</term><term>Phosphites</term></keywords><keywords scheme="MESH" qualifier="analogues et dérivés" xml:lang="fr"><term>Désoxycytidine</term></keywords><keywords scheme="MESH" qualifier="synthèse chimique" xml:lang="fr"><term>Oligodésoxyribonucléotides</term><term>Oligonucléotides</term></keywords><keywords scheme="MESH" xml:lang="en"><term>Models, Molecular</term><term>Phosphorylation</term><term>Thermodynamics</term></keywords><keywords scheme="MESH" xml:lang="fr"><term>ADN</term><term>Composés organiques du phosphore</term><term>Désoxyadénosine</term><term>Désoxycytidine</term><term>Modèles moléculaires</term><term>Oligodésoxyribonucléotides</term><term>Oligonucléotides</term><term>Phosphites</term><term>Phosphorylation</term><term>Thermodynamique</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Previously, O-selective phosphorylation on polymer supports in the N-unprotected phosphoramidite method could not be carried out because the amino groups of dA and dC have high reactivity toward tervalent phosphorus(III)-type phosphitylating reagents. In this paper, we developed a new coupling strategy named the "activated phosphite method" in which the phosphitylation is mediated by phosphite triester intermediates 1. Application of 1-hydroxybenzotriazole as the promoter to the solid-phase synthesis resulted in excellent O-selectivity of more than 99.7%. This O-selectivity was explained by the frontier molecular orbital interactions between the reactive intermediates and the nucleophiles such as the amino or hydroxyl groups of nucleosides. Furthermore, longer oligonucleotides were synthesized not only by a manual operation but also by a DNA synthesizer. The utility of our new method was demonstrated by the successful synthesis of a base-labile modified oligodeoxyribonucleotide having 4-N-acetyldeoxycytidine residues. Finally, DNA 20-mers containing dA or dC could be synthesized in good yields by use of a combined reagent of 6-trifluoromethyl-1-hydroxybenzotriazole and benzimidazolium triflate.</div></front></TEI></record>Pour manipuler ce document sous Unix (Dilib)
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