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- W2017883606 abstract "Die (2′→ 5′)- und (3′→ 5′)-verknüpften Dinucleosid-monophosphate 3e und 2e des Tubercidins werden aus den Vorstufen 1b oder 1c und 1a durch Kondensation mit Dichlormethoxyphosphan erhalten. Mit 1H-NMR-Untersuchungen konnte gezeigt werden, daß die Nucleobasen eine andere Konformation als im (2′→ 5′)- oder (3′→ 4′)ApA einnehmen. Aus thermodynamischen Parametern sowie der Hypochromizität ergibt sich für 3e eine größere Basenwechselwirkung als für 2e. Einzelstrang-spezifische Nuclease S1 spaltet 2e deutlich schneller als (3′→ 5′)ApA und reagiert damit empfindlich auf die Aglyconmodifikation. Die Kondensation des 5′-entschützten Dimers 3b mit dem Monomer 1c, gefolgt von der Abspaltung der Schutzgruppen, führt zu (2′→ 5′)-TupTupTu (4e). Dies stellt ein Analogon von (2′→ 5′)ApApA dar, das als Triphosphat antiviral wirksam ist. (2′→5′) and (3′→′)-Tubercidylyl-tubercidins - Synthesis via Phosphite Triester and Investigation of Secondary Structure The (2′→ 5′)- and (3′→5′)-linked dinucleoside monophosphates 3e and 2e of tubercidin were synthesized by condensation of the monomers 1c or 1b with dichloromethoxyphosphane. By 1H NMR studies it could be demonstrated that the conformation of these nucleobases is different from that in (3′→ 5′)ApA and (2′→ 5′)ApA. From thermodynamic parameters, as well as from hypochromicity, a stronger base – base interaction in 3e than in 2e was deduced. Single-strand specific nuclease S1 hydrolyses 2e at a much higher rate than (3′→ 5′)ApA demonstrating that the enzyme is sensitive towards modification of the aglycone. Condensation of the 5′-deprotected dimer 3b with the monomer 1c followed by complete deprotection yields (2′→ 5′)TupTuTu (4e), which is an analogue of (2′→ 5′)ApApA, the triphosphate of which is antivirally active." @default.
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- W2017883606 title "(2′→ 5′)- und (3′→ 5′)- Tubercidylyl-tubercidine – Synthese über Phosphit- Triester und Untersuchungen zur Sekundärstruktur," @default.
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