Mechanistic Investigations into the Application of Sulfoxides in Carbohydrate Synthesis.
Mechanistic Investigations into the Application of Sulfoxides in Carbohydrate Synthesis.
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DOI：
10.1002/chem.201503504
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发表时间：
2016-03-14
期刊：
影响因子：
--
通讯作者：
Turnbull WB
中科院分区：
文献类型：
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作者：
Fascione MA;Brabham R;Turnbull WB
自从 1989 年首次引入亚砜作为糖基供体以来，亚砜在碳水化合物化学领域的各种转化中的应用得到了快速增长。从那时起，亚砜已不仅仅是异头离去基团，如今在糖基化反应中具有多种作用。这些包括作为硫代糖苷、半缩醛和糖醛的活化剂，以及作为糖基三氟甲磺酸酯的前体，这对于立体选择性 β-甘露糖苷合成至关重要，以及促进 α-糖苷立体选择性合成的双环锍离子。在这篇综述中，我们重点介绍了在这一领域进行的机制研究，通常概述了用于区分多种拟议反应途径的策略，以及这些研究的结论如何已经并将继续为基于亚砜的碳水化合物合成中更有效的转化的发展提供信息。
The utility of sulfoxides in a diverse range of transformations in the field of carbohydrate chemistry has seen rapid growth since the first introduction of a sulfoxide as a glycosyl donor in 1989. Sulfoxides have since developed into more than just anomeric leaving groups, and today have multiple roles in glycosylation reactions. These include as activators for thioglycosides, hemiacetals, and glycals, and as precursors to glycosyl triflates, which are essential for stereoselective β‐mannoside synthesis, and bicyclic sulfonium ions that facilitate the stereoselective synthesis of α‐glycosides. In this review we highlight the mechanistic investigations undertaken in this area, often outlining strategies employed to differentiate between multiple proposed reaction pathways, and how the conclusions of these investigations have and continue to inform upon the development of more efficient transformations in sulfoxide‐based carbohydrate synthesis.