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Promotion of a Reaction by Cooling: Stereoselective 1,2‐ cis ‐α‐Thioglycoconjugation by Thiol‐Ene Coupling at −80 °C
Author(s) -
Eszenyi Dániel,
Kelemen Viktor,
Balogh Fanny,
Bege Miklós,
Csávás Magdolna,
Herczegh Pál,
Borbás Anikó
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800668
Subject(s) - stereoselectivity , chemistry , ene reaction , coupling reaction , selectivity , thiol , thio , stereochemistry , medicinal chemistry , catalysis , organic chemistry
Abstract The photoinitiated thiol‐ene coupling reactions of 2‐substituted glycals were studied as a generally applicable strategy for stereoselective 1,2‐ cis ‐α‐thioconjugation. Although all glycals reacted with full α‐selectivity, the efficacy of the reactions varied in a broad range depending on their configuration and glycals bearing axial acetoxy substituents reacted with very low efficacy at room temperature. The study revealed that the reaction progress could be promoted by cooling and inhibited by heating. At −80 °C, the equilibrium of the rapidly reversible addition of the thiyl radical to alkenes is shifted almost completely toward products, leading to efficient addition reactions. By exploiting this unique temperature effect a series of α‐thio‐ l ‐fucosides, ‐ d ‐galactosides, and d ‐GlcNAc derivatives were prepared with high efficacy and complete stereoselectivity.