Site-selective redox isomerizations of furanosides using a combined arylboronic acid/photoredox catalyst system. Issue 6 (3rd January 2020)

• Record Type: Journal Article
• Authors: Dimakos, Victoria; Gorelik, Daniel; Su, Hsin Y.; Garrett, Graham E.; Hughes, Gregory; Shibayama, Hiromitsu; Taylor, Mark S.
• Is Part Of: Chemical science. Volume 11:Issue 6(2020)
• Page Start: 1531
• Page End: 1537
• Publication Date: 2020-01-03
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c9sc05173b
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : The combined action of boronic acid, photoredox catalyst and hydrogen atom transfer mediator enables the transformation of furanosides to 2-keto-3-deoxyfuranosides, a synthetic analog of the process catalyzed by the ribonucleotide reductase enzymes. 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.