Corcé Vincent, McSweeney Lauren, Malone Aoife, Scanlan Eoin M
School of Chemistry, Trinity Biomedical Sciences Institute, Trinity College, 152-160 Pearse Street, Dublin 2, Ireland.
Chem Commun (Camb). 2015 May 21;51(41):8672-4. doi: 10.1039/c5cc02162f.
A novel intramolecular thiol-yne cyclisation strategy has been developed for the synthesis of thioglycals. Both ionic and radical mediated cyclisation pathways have been investigated for D- and L-sugars. The ionic cyclisation provides exclusive access to 5-exo products directly from the thioesters whereas the radical cyclisation provides access to both 5-exo and 6-endo products upon photochemical irradiation of the free thiols. These are the first examples of intramolecular thiol-yne cyclisation reactions applied to thiosugar synthesis.
已开发出一种用于合成硫代糖苷的新型分子内硫醇-炔环化策略。已针对D-糖和L-糖研究了离子介导和自由基介导的环化途径。离子环化可直接从硫酯中独家获得5-外向型产物，而自由基环化在对游离硫醇进行光化学辐照时可获得5-外向型和6-内向型产物。这些是应用于硫代糖合成的分子内硫醇-炔环化反应的首个实例。
