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

Victoria Dimakos; Daniel Gorelik; Hsin Y. Su; Graham E. Garrett; Gregory Hughes; Hiromitsu Shibayama; Mark S. Taylor

doi:10.1039/C9SC05173B

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

Victoria Dimakos,‡^a Daniel Gorelik,‡^a Hsin Y. Su,^a Graham E. Garrett,

^a Gregory Hughes,^b Hiromitsu Shibayama^a and Mark S. Taylor

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry, University of Toronto, 80 St. George St., Toronto, ON M5S 3H6, Canada
E-mail: mtaylor@chem.utoronto.ca

^b Global Process Chemistry, Merck Research Laboratories, P. O. Box 2000, Rahway, NJ 07065, USA

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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Article information

DOI: https://doi.org/10.1039/C9SC05173B
Article type: Edge Article
Submitted: 11 Oct 2019
Accepted: 12 Dec 2019
First published: 03 Jan 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2020,11, 1531-1537

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

V. Dimakos, D. Gorelik, H. Y. Su, G. E. Garrett, G. Hughes, H. Shibayama and M. S. Taylor, Chem. Sci., 2020, 11, 1531 DOI: 10.1039/C9SC05173B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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Chemical Science

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

Abstract

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

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