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Modeling of the ribonucleotide reductases substrate reaction. Hydrogen atom abstraction by a thiyl free radical and detection of the ribosyl-based carbon radical by pulse radiolysis
Stanislaw F. Wnuk, Jaidev A. K. Penjarla, Thao Dang, Alexander M. Mebel, Thomas Nauser and Christian Schöneich
Jazyk angličtina Země Česko Médium elektronický zdroj
The 1,4-anhydro-5-deoxy-6-thio-D-ribo-hexofuranitol (1) was prepared from 1,2-O-isopropylidene-α-D-glucose in 10 steps. In a key step treatment of the 1,2-O-isopropylidenehexofuranose derivative with BF3/Et3SiH effected deacetonization and reductive deoxygenation at carbon 1. Pulse radiolysis experiments with 6-thiohexofuranitol 1 and its disulfide derivative demonstrated formation of the ribosyl-based carbon-centered radical upon generation of 6-thiyl radical in basic medium. The proposed [1,5]-hydrogen shift abstraction with generation of the C3 radical mimics the initial substrate reaction of RNRs. The reversible H-atom transfer has been quantified and was correlated with the computed rate constants for the internal H atom abstraction from C1, C2, C3 and C4 by the thiyl radical. The energy barrier for the H3 and H4 abstractions were calculated to be most favorable with the corresponding barriers of 11.1 and 11.2 kcal/mol, respectively.
Department of Chemistry and Applied Bioscience ETH Zurich CH 8093 Switzerland
Department of Chemistry and Biochemistry Florida International University Miami Florida 33199 USA
Department of Pharmaceutical Chemistry University of Kansas Lawrence Kansas 66047 USA
Modeling of the ribonucleotide reductases substrate reaction. Hydrogen atom abstraction by a thiyl free radical and detection of the ribosyl-based carbon radical by pulse radiolysis [elektronický zdroj] /
Citace poskytuje Crossref.org
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- $a Modeling of the ribonucleotide reductases substrate reaction. Hydrogen atom abstraction by a thiyl free radical and detection of the ribosyl-based carbon radical by pulse radiolysis $h [elektronický zdroj] / $c Stanislaw F. Wnuk, Jaidev A. K. Penjarla, Thao Dang, Alexander M. Mebel, Thomas Nauser and Christian Schöneich
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- $a The 1,4-anhydro-5-deoxy-6-thio-D-ribo-hexofuranitol (1) was prepared from 1,2-O-isopropylidene-α-D-glucose in 10 steps. In a key step treatment of the 1,2-O-isopropylidenehexofuranose derivative with BF3/Et3SiH effected deacetonization and reductive deoxygenation at carbon 1. Pulse radiolysis experiments with 6-thiohexofuranitol 1 and its disulfide derivative demonstrated formation of the ribosyl-based carbon-centered radical upon generation of 6-thiyl radical in basic medium. The proposed [1,5]-hydrogen shift abstraction with generation of the C3 radical mimics the initial substrate reaction of RNRs. The reversible H-atom transfer has been quantified and was correlated with the computed rate constants for the internal H atom abstraction from C1, C2, C3 and C4 by the thiyl radical. The energy barrier for the H3 and H4 abstractions were calculated to be most favorable with the corresponding barriers of 11.1 and 11.2 kcal/mol, respectively.
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