Nucleic acid related compounds.: 108.: 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

被引：9

作者：

Guo, ZQ ^{[1
]}

Samano, MC ^{[1
]}

Krzykawski, JW ^{[1
]}

Wnuk, SF ^{[1
]}

Ewing, GJ ^{[1
]}

Robins, MJ ^{[1
]}

机构：

[1] Brigham Young Univ, Dept Chem & Biochem, Provo, UT 84602 USA

来源：

TETRAHEDRON | 1999年 / 55卷 / 18期

关键词：

biomimetic reactions; carbohydrates; enzymes and enzyme reactions; radicals and radical reactions;

D O I：

10.1016/S0040-4020(99)00238-0

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Generation of 6-oxyl radicals from homoribofuranose (5-deoxy-D-ribo-hexofuranose) 6-O-nitro esters with Bu3SnD/AIBN/benzene/Delta resulted in abstraction of H3 by a [1,5]-hydrogen atom shift. Transfer of H-2 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'. (C) 1999 Elsevier Science Ltd. All rights reserved.

引用

页码：5705 / 5718

页数：14

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