Systematic study on free radical hydrothiolation of unsaturated monosaccharide derivatives with exo- and endocyclic double bonds

László Lázár, Magdolna Csávás, Ádám Hadházi, Mihály Herczeg, M. Tóth, L. Somsák, Terézia Barna, P. Herczegh, A. Borbás

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Exo- and endocyclic double bonds of glycals and terminal double bonds of enoses were reacted with various thiols by irradiation with UV light in the presence of a cleavable photoinitiator. The photoinduced radical-mediated hydrothiolation reactions showed highly varying overall conversions depending not only on the substitution pattern and electron-density of the double bond but also on the nature and substitution pattern of the thiol partner. Out of the applied thiols thiophenol, producing the highly stabilized thiyl radical, exhibited the lowest reactivity toward each type of alkene. In most cases, the hydrothiolations took place with full regio- and stereoselectivities. Successful addition of 1,2:3,4-di-O-isopropylidene-6-thio-α-d-galactopyranose to a 2,3-unsaturated N-acetylneuraminic acid derivative, providing a (3 → 6)-S-linked pseudodisaccharide, demonstrated that the endocyclic double bond of Neu5Ac-2-ene, bearing an electron-withdrawing substituent, shows sufficient reactivity in the photoinduced thiol-ene coupling reaction.

Original languageEnglish
Pages (from-to)5339-5350
Number of pages12
JournalOrganic and Biomolecular Chemistry
Volume11
Issue number32
DOIs
Publication statusPublished - Aug 28 2013

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monosaccharides
Monosaccharides
Sulfhydryl Compounds
thiols
free radicals
Free Radicals
Derivatives
Substitution reactions
Bearings (structural)
reactivity
Electrons
substitutes
Stereoselectivity
Regioselectivity
Alkenes
N-Acetylneuraminic Acid
Ultraviolet Rays
Galactose
Ultraviolet radiation
alkenes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Biochemistry

Cite this

Systematic study on free radical hydrothiolation of unsaturated monosaccharide derivatives with exo- and endocyclic double bonds. / Lázár, László; Csávás, Magdolna; Hadházi, Ádám; Herczeg, Mihály; Tóth, M.; Somsák, L.; Barna, Terézia; Herczegh, P.; Borbás, A.

In: Organic and Biomolecular Chemistry, Vol. 11, No. 32, 28.08.2013, p. 5339-5350.

Research output: Contribution to journalArticle

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