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[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Site-selective redox isomerizations of furanosides using a combined arylboronic acid/photoredox catalyst system
Victoria Dimakos1, Daniel Gorelik1, Hsin Y Su1
1Department of Chemistry, University of Toronto 80 St. George St. Toronto ON M5S 3H6 Canada mtaylor@chem.utoronto.ca.
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.
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