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Studies on the Stereoselective Synthesis of Deuterated D ‐Ribose Derivatives
Author(s) -
Kundu Mrinal K.,
Földesi Andras,
Chattopadhyaya Jyoti
Publication year - 2003
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200390062
Subject(s) - chemistry , stereoselectivity , stereochemistry , moiety , ribose , deuterium , enantiomer , nuclear magnetic resonance spectroscopy , heteronuclear molecule , walden inversion , stereospecificity , organic chemistry , physics , quantum mechanics , enzyme , catalysis
In view of the importance of the site‐specific substitution of the H‐atom by its stable isotope 2 H in a stereoselective/stereospecific manner at the pentose sugar residue, decreasing the spectral overcrowding in various regions of 1D and 2D homo‐ and heteronuclear correlation spectra of oligo‐DNA and ‐RNA, there is always a need for the development of new methods for the incorporation of 2 H at different sites of a ribose. High‐yielding multistep syntheses of C(2)‐, and (5 R )‐ and (5 S )‐3,5‐deuterated ribose derivatives have been envisaged for the application of site‐specific incorporation of multilabeled nucleosides into oligomers to facilitate their structure elucidation by NMR spectroscopy. All syntheses started from D ‐glucose after proper derivatization. In the case of C(2), >97 atom‐% isotope was incorporated, employing an inversion of the configuration at C(2) as the key reaction. For C(5), two different routes were envisaged: on the one hand, deuterated achiral reagent was treated with a conformationally locked sugar moiety 15 , while, on the other, chiral protonated sources were used to transfer the H‐atom to a C(5)‐deuterated aldehyde 18 . In all cases, enantiomeric and isotopic purities were found to be as high as >97% as determined by NMR spectroscopy.