Elsevier

Tetrahedron

Volume 55, Issue 18, 30 April 1999, Pages 5705-5718
Tetrahedron

Biomimetic modeling of the abstraction of H3′ by ribonucleotide reductases. 1,5-Hydrogen atom transfer of H3 to aminyl and oxyl, but not thiyl, free radicals in homoribofuranose derivatives

https://doi.org/10.1016/S0040-4020(99)00238-0Get rights and content

Abstract

Generation of 6-oxyl radicals from homoribofuranose (5-deoxy-D-ribo-hexofuranose) 6-O-nitro esters with Bu3SnD/AIBN/benzene/Δ resulted in abstraction of H3 by a [1,5]-hydrogen atom shift. Transfer of 2H from the stannane to •C3 effected incorporation of deuterium at C3. Analogous treatment of 6-azido-6-deoxy-D-ribo-hexofuranose derivatives gave C3-deuterated aminosugars. In contrast, no deuterium incorporation was detected upon parallel treatment of 6-thio-D-ribo-hexofuranose derivatives. Abstraction of H3′ by a thiyl radical (•SCys) is the postulated first step in reactions that are utilized by ribonucleotide reductases to convert ribonucleotides into 2′-deoxynucleotides. Results are discussed relative to the enzyme reaction cascade that couples abstraction of H3′ with irreversible loss of water from C2′.

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    Nucleic Acid Related Compounds. 108. Paper 107 is: Giziewicz, J.; Wnuk, S. F.; Robins, M. J. J. Org. Chem., in press.

    Present address: Neurocrine Biosciences, San Diego, CA.

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    Present address: Department of Chemistry, Florida International University, Miami, FL.

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