Behaviour of some 1-C-acceptor-substituted glycals under azidohydroxylation conditions

Ágnes Homolya; Ivett Jedlóczki; Anita Kónya-Ábrahám; László Somsák; Marietta Tóth; László Juhász

doi:10.1016/j.carres.2023.108825

Behaviour of some 1-C-acceptor-substituted glycals under azidohydroxylation conditions

Carbohydr Res. 2023 Jul:529:108825. doi: 10.1016/j.carres.2023.108825. Epub 2023 Apr 27.

Authors

Ágnes Homolya¹, Ivett Jedlóczki², Anita Kónya-Ábrahám², László Somsák², Marietta Tóth², László Juhász³

Affiliations

¹ Department of Organic Chemistry, University of Debrecen, PO Box 400, H-4002, Debrecen, Hungary; University of Debrecen, Doctoral School of Chemistry, PO Box 400, H-4002, Debrecen, Hungary.
² Department of Organic Chemistry, University of Debrecen, PO Box 400, H-4002, Debrecen, Hungary.
³ Department of Organic Chemistry, University of Debrecen, PO Box 400, H-4002, Debrecen, Hungary. Electronic address: juhasz.laszlo@science.unideb.hu.

PMID: 37253301
DOI: 10.1016/j.carres.2023.108825

Abstract

Azidohydroxylation of 1-carbamoyl, 1-methoxycarbonyl and 1-cyano substituted d-lyxo and d-arabino configured O-peracylated glycals was studied and the reaction conditions were optimized. Under these conditions (3 equiv. NaN₃/2 equiv. PIFA/0.3 equiv. TEMPO/50 equiv. H₂O/dry DCM/0 °C/Ar) the expected 3-azido-3-deoxy ulopyranosonic acid derivatives were isolated in good yield with α-d-galacto configuration exclusively from the reaction of the 1-carbamoyl and 1-methoxycarbonyl substituted d-lyxo configured O-peracetylated glycals, while the transformation of the 1-cyano derivative gave a 2,3-vicinal diazide in low yield. The 1-carbamoyl d-arabino configured O-perbenzoylated glycal gave a mixture of α-d-gluco and α-d-manno configured azidohydroxylated products with d-gluco preference. The analogous 1-methoxycarbonyl derivative gave an inseparable product mixture and no transformation was detected with the respective 1-cyano glycal.

Keywords: 1-C-acceptor substituted glycals; 2-azido-2-dezoxy-sugar; Azidohydroxylation; PIFA.