Reactions of 1-C-acceptor-substituted glycals with nucleophiles under acid promoted (Ferrier-rearrangement) conditions

Levente Homolya; Dávid Antal; Máté Nagy; Éva Juhász-Tóth; Marietta Tóth; Attila Bényei; László Somsák; László Juhász

doi:10.1016/j.carres.2022.108582

Reactions of 1-C-acceptor-substituted glycals with nucleophiles under acid promoted (Ferrier-rearrangement) conditions

Carbohydr Res. 2022 Sep:519:108582. doi: 10.1016/j.carres.2022.108582. Epub 2022 May 10.

Authors

Levente Homolya¹, Dávid Antal², Máté Nagy², Éva Juhász-Tóth², Marietta Tóth², Attila Bényei³, László Somsák², László Juhász⁴

Affiliations

¹ Department of Organic Chemistry, University of Debrecen, POB 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, POB 400, H-4002, Debrecen, Hungary.
³ Department of Physical Chemistry, University of Debrecen, POB 400, H-4002, Debrecen, Hungary.
⁴ Department of Organic Chemistry, University of Debrecen, POB 400, H-4002, Debrecen, Hungary. Electronic address: juhasz.laszlo@science.unideb.hu.

PMID: 35704963
DOI: 10.1016/j.carres.2022.108582

Abstract

The reactivity of O-peracetylated and O-perbenzoylated 1-COOMe, 1-CONH₂ and 1-CN-substituted glycals was studied against O-, S-, N- and C-nucleophiles in the presence of Lewis acids. Allylic substituted products with exclusive axial stereoselectivity were formed with simple alcohols, N₃^-, and Cl^- ions, but with benzyl thiol the Ferrier rearrangement took place and thioglycosides were obtained. The use of a sugar derived thiol resulted in the formation of both the allylic substituted and the rearranged products.

Keywords: 1-C-Substituted glycals; Allylic substitution; Ferrier rearrangement; Lewis acids.

MeSH terms

Alcohols
Carbohydrates
Stereoisomerism
Sulfhydryl Compounds
Thioglycosides*

Substances

Alcohols
Carbohydrates
Sulfhydryl Compounds
Thioglycosides