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高反应性的2-脱氧-2-碘-D-吡喃糖基亚砜供体可确保与甾体苷元进行β-立体选择性糖基化反应。

Highly reactive 2-deoxy-2-iodo-d- and d- pyranosyl sulfoxide donors ensure β-stereoselective glycosylations with steroidal aglycones.

作者信息

Mestre Jordi, Collado David, Benito-Alifonso David, Rodríguez Miguel A, Matheu M Isabel, Díaz Yolanda, Castillón Sergio, Boutureira Omar

机构信息

Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili C/Marcel·lí Domingo 1 43007 Tarragona Spain

出版信息

RSC Adv. 2018 Aug 24;8(53):30076-30079. doi: 10.1039/c8ra06619a.

DOI:10.1039/c8ra06619a
PMID:35546863
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9085402/
Abstract

The preparation of well-defined d- and d- glycosides represents a synthetic challenge due to the limited configurational availability of starting materials and the laborious synthesis of homogeneous 2-deoxy-β-glycosidic linkages, in particular that of the sugar-steroid motif, which represents the "stereoselective determining step" of the overall synthesis. Herein we describe the use of 2-deoxy-2-iodo-glycopyranosyl sulfoxides accessible from widely available d-xylose and d-ribose monosaccharides as privileged glycosyl donors that permit activation at very low temperature. This ensures a precise kinetic control for a complete 1,2- stereoselective glycosylation of particularly challenging steroidal aglycones.

摘要

由于起始原料的构型可用性有限以及均相2-脱氧-β-糖苷键的合成过程繁琐，特别是糖-甾体基序的合成，其代表了整个合成的“立体选择性决定步骤”，因此制备结构明确的d-和d-糖苷是一项合成挑战。在此，我们描述了使用可从广泛可得的d-木糖和d-核糖单糖获得的2-脱氧-2-碘代吡喃糖基亚砜作为特殊的糖基供体，其允许在非常低的温度下活化。这确保了对特别具有挑战性的甾体苷元进行完全的1,2-立体选择性糖基化的精确动力学控制。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6be8/9085402/3071d5e3e703/c8ra06619a-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6be8/9085402/40cb6bf4b078/c8ra06619a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6be8/9085402/c3235ece0911/c8ra06619a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6be8/9085402/179b58553819/c8ra06619a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6be8/9085402/3071d5e3e703/c8ra06619a-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6be8/9085402/40cb6bf4b078/c8ra06619a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6be8/9085402/c3235ece0911/c8ra06619a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6be8/9085402/179b58553819/c8ra06619a-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6be8/9085402/3071d5e3e703/c8ra06619a-s3.jpg

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