Hydrolysis of thymidine boranomonophosphate and stepwise deuterium substitution of the borane hydrogens. 31P and 11B NMR studies
The α-P-boranophosphate nucleosides comprise a new class of modified nucleotides that may find use as therapeutic and DNA diagnostic agents. Hydrolysis of thymidine 5'-boranomonophosphate, d(p(B)T), has been studied in H2O and D2O using 1H, 31P, and 11B NMR spectroscopies. Although d(p(B)T) is quite stable at 25 °C, it hydrolyzes slowly at higher temperatures. At 50 or 60 °C, d(p(B)T) hydrolyzes first into thymidine (dT) and boranophosphate (O3P-BH33-), followed by subsequent hydrolysis of the O3P-BH33- to produce phosphonate and boric acid. A three-step deuterium substitution of the borane hydrogens in O3P-BH33- was detected in D2O by the presence of a 31P isotope shift. The 31P resonances shifted downfield by 0.14 ppm upon substitution of each of three 1H atoms by 2H. Exchange of the borane hydrogens with D2O occurs as sequential processes superimposed upon hydrolysis of O3P-BH33-. The hydrolysis and deuteration steps were characterized in terms of pseudo-first-order rate constants. Hydrolysis of O3P-BH33- is an order of magnitude slower than deuterium substitution.
Duke Scholars
Altmetric Attention Stats
Dimensions Citation Stats
Published In
DOI
ISSN
Publication Date
Volume
Issue
Start / End Page
Related Subject Headings
- General Chemistry
- 40 Engineering
- 34 Chemical sciences
- 03 Chemical Sciences
Citation
Published In
DOI
ISSN
Publication Date
Volume
Issue
Start / End Page
Related Subject Headings
- General Chemistry
- 40 Engineering
- 34 Chemical sciences
- 03 Chemical Sciences