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Site-selective redox isomerizations of furanosides using a combined arylboronic acid/photoredox catalyst system.

ABSTRACT: In the presence of an arylboronic acid and a hydrogen atom transfer mediator under photoredox conditions, furanoside derivatives undergo site-selective redox isomerizations to 2-keto-3-deoxyfuranosides. Experimental evidence and computational modeling suggest that the transformation takes place by abstraction of the hydrogen atom from the 2-position of the furanoside-derived arylboronic ester, followed by C3-O bond cleavage via spin-center shift. This mechanism is reminiscent of the currently accepted pathway for the formation of 3'-ketodeoxynucleotides by ribonucleotide reductase enzymes.

SUBMITTER: Dimakos V

PROVIDER: S-EPMC8148048 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Site-selective redox isomerizations of furanosides using a combined arylboronic acid/photoredox catalyst system.

Dimakos Victoria V Gorelik Daniel D Su Hsin Y HY Garrett Graham E GE Hughes Gregory G Shibayama Hiromitsu H Taylor Mark S MS

Chemical science 20200103 6

In the presence of an arylboronic acid and a hydrogen atom transfer mediator under photoredox conditions, furanoside derivatives undergo site-selective redox isomerizations to 2-keto-3-deoxyfuranosides. Experimental evidence and computational modeling suggest that the transformation takes place by abstraction of the hydrogen atom from the 2-position of the furanoside-derived arylboronic ester, followed by C3-O bond cleavage <i>via</i> spin-center shift. This mechanism is reminiscent of the curre ...[more]

PMID: 34084383

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