Synthesis and Structure of New Methylene-bridged hexopyranosyl nucleoside (BHNA)

• A new member of hexopyranosyl nucleoside family, methylene-bridged   hexopyranosyl nucleoside (BHNA), has been synthesized through   generation of carbon radical at C6' in [6'S-Me, 7'S-Me]-carba-LNA T  nucleoside, followed by rearrangement to C4' radical which was quenched   by hydrogen atom to give BHNA. The stereoelectronic requirement for   this unusual radical rearrangement has been elucidated by chemical   model building and ab intio calculations to show that the coplanarity of the single electron occupied p-orbital at C6' with sigma*(O4'-C4')   plays an important role for the rearrangement reaction to take place.   The solution structure of BHNA has also been studied using NMR as well   as by ab initio calculations. The new six-membered pyranosyl ring in  BHNA, unlike other known hexopyranosyl nucleosides, adopts a twist   conformation, with base moiety occupying the axial position while  3'-hydroxymethyl and 4'-hydroxyl occupying the equatorial position.

Ämnesord

NATURVETENSKAP  -- Biologi (hsv//swe)

NATURAL SCIENCES  -- Biological Sciences (hsv//eng)

Nyckelord

Conformationally Constrained Nucleoside

Hexopyranosyl Nucleoside

Radical Rearrangement

Conformational Analysis

ab initio Calculation

Biology

Biologi

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