Moya-López Juan Francisco, Elhalem Eleonora, Recio Rocío, Álvarez Eleuterio, Fernández Inmaculada, Khiar Noureddine
Instituto de Investigaciones Químicas, C.S.I.C-Universidad de Sevilla, c/. Américo Vespucio, 49., Isla de la Cartuja, 41092 Sevilla, Spain.
Org Biomol Chem. 2015 Feb 14;13(6):1904-14. doi: 10.1039/c4ob02030h.
A detailed study on the diastereoselective oxidation of 1-thio-β-D-glucopyranosides is reported. It has been shown that the sense and the degree of stereochemical outcome of the oxidation are highly dependent on the substituent of the sulfur and on the protective group of the C2-OH. In the case of thioglycosides with a bulky aglycone, the mesylation of C2-OH has a significant effect on the stereochemical outcome of the oxidation, affording the usually less favoured RS sulfoxide as a single diastereoisomer. The absolute configuration of the final sulfinyl glycosides was ascertained by NMR analysis and corroborated by X-ray crystallography.
报道了关于1-硫代-β-D-吡喃葡萄糖苷非对映选择性氧化的详细研究。结果表明，氧化反应的立体化学结果的方向和程度高度依赖于硫的取代基以及C2-OH的保护基团。对于具有庞大糖苷配基的硫代糖苷，C2-OH的甲磺酰化对氧化反应的立体化学结果有显著影响，以单一非对映异构体形式提供通常较不稳定的RS亚砜。最终亚磺酰基糖苷的绝对构型通过核磁共振分析确定，并通过X射线晶体学得到证实。
