"超级武装"的甘氨基基捐赠体:通过化来对硫甘氨基酸的构造性武装
Christian Marcus Pedersen1, Lars Ulrik Nordstrøm, Mikael Bols
1Department of Chemistry, University of Aarhus, Langelandsgade 140, DK-8000 Aarhus C, Denmark.
Journal of the American Chemical Society
|July 3, 2007
概括
大量的西里尔保护群 (TBS) 增强了甘氨酸供体的反应性,使复杂碳水化合物的有效合成成为可能. 这一突破为创造碳水化合物合成的"超级武装"捐赠者和接受者提供了新的战略.
科学领域:
- 碳水化合物化学 碳水化合物化学
- 有机合成 有机合成
- 立体化学是一种立体化学.
背景情况:
- 糖化反应是碳水化合物化学的基础.
- 开发高效的甘氨基基捐赠体对于合成复杂的寡糖至关重要.
- 传统的保护小组可以限制捐赠者的反应性和立体选择性.
研究的目的:
- 为了研究庞大的西利尔保护群对甘氨酸供体反应性的影响.
- 探索控制增强反应性的立体电子效应.
- 建立一个创建高反应性甘氨酸供体和接受体的策略.
主要方法:
- 用 tert-butyldimethylsilyl (TBS) 组保护的硫糖化物供体的合成.
- 对TBS受保护的捐赠体与基化硫糖化物进行比较.
- 使用计算或光谱方法 (隐含) 分析形状变化和立体电子效应.
- "超级武装"的捐赠者和接受者之间的交叉合反应.
主要成果:
- 与基化对应物相比,受TBS保护的甘氨基基捐赠者表现出更高的反应性.
- 增强的反应性归因于来自化诱导的形状变化的立体电子效应.
- 在过渡状态下,TBS捐赠者采用与轴向OR组的构造,有利于电荷双极相互作用.
- 通过使用TBS保护的捐赠体和武装接受体,成功合成武装分糖体以良好的到优秀的产量.
结论:
- 大量的西保护组,特别是TBS,显著增强了糖捐赠者的反应性.
- 由TBS群体所施加的 conformational 控制为糖化提供了一个强大的工具.
- 这种方法可以创建"超级武装"的捐赠者和接受者,以有效合成复杂碳水化合物.
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