通过用异酸盐对氧化物进行N-选择性碳化生成的N-碳酸的分子间1,3-双极循环添加反应
Ayaka Yamamoto1, Kosaku Tanaka1,2, Yoshimitsu Hashimoto1
1Showa Pharmaceutical University, Higashi-Tamagawagakuen, 194-8543, Machida, Tokyo, Japan.
Chemistry (Weinheim an der Bergstrasse, Germany)
|December 6, 2023
概括
这项研究引入了一种新方法,用于通过氧化物和异酸盐的子形成合成异酸,然后再循环添加. 获得了高产量,替代物是可移除的,计算研究阐明了机制.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 子是有机合成中的多功能中间体.
- 1,3-双极循环添加反应对于形成异环化合物至关重要.
- 异索利丁是重要的异环基架,具有多样化的应用.
研究的目的:
- 开发一种新型的N选择性碳amylation反应的oximes与异酸盐产生子.
- 为了研究这些子的随后的1,3-双极循环添加与各种双极性质的异索利丁合成.
- 探索异素替代剂的降解保护,阐明反应机制和立体选择性.
主要方法:
- 使用异酸盐对氧化物进行N选择性碳amylation.
- 1,3-双极循环添加反应与不同的双极性质.
- 对N替代物的化学降解保护.
- 密度函数理论 (DFT) 计算用于机械学和立体选择性研究.
主要成果:
- 从氧化物和异酸盐建立了一个新的合成路径,以获得来自氧化物和异酸盐的.
- 通过1,3-双极循环添加,通过高产量 (高达94%) 合成了各种异佐利丁.
- 在不损害循环结构的情况下,可以去除异佐利丁环上的N替代物.
- 计算研究成功阐明了反应机制和立体选择性的起源.
结论:
- 开发的方法提供了一种高效和多功能途径,用于合成替代的异二.
- 反应的高反应性,特别是与富含电子的氧化物和缺乏电子的双极分子,提供了显著的合成优势.
- 能够去除N替代物的能力提高了合成的异佐利丁的效用,以进一步功能化.
- 从计算研究中获得的机械洞察力将指导未来的反应优化和开发.
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