氧-循环添加反应:可逆形成1,2-氧和六成员异循环
Pawel Löwe1, Milica Feldt2, Marius A Wünsche1
1Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstraße 30, 48149 Münster, Germany.
Journal of the American Chemical Society
|May 5, 2020
概括
氧离子通过 [2 + 2] 循环添加与反应,形成新的1,2-氧离子. 这些中间体可以进一步转化为有价值的六合异环,扩大合成可能性.
科学领域:
- 有机化学
- 有机化学
- 主组化学
背景情况:
- 涉及和碳化合物的转化反应是有机合成的基石.
- 异电子主组R2EO化合物的与基的反应性在很大程度上仍未被探索.
- 氧离子作为碳化合物的同源.
研究的目的:
- 研究氧离子和之间的循环添加反应.
- 探索由此产生的含异环的合成实用性.
- 阐明这些系统中控制氧原子转移的电子因素.
主要方法:
- 氧离子与各种之间的 [2 + 2] 循环添加反应.
- 1,2-氧离子的隔离和结构特征.
- 热环开放的异环,形成异基中间体.
- 用于合成六个成员异环的Hetero Diels-Alder反应.
- 量子化学计算以研究反应机制和替代物效应.
主要成果:
- 氧离子与酸盐的成功 [2 + 2] 循环添加形成1,2-氧离子.
- 这些新型压力-氧异环体的隔离和完整结构特征.
- 热环开放到异中间体的演示
- 随后的异质迪尔斯-阿尔德反应使多种六成员异质环的合成成为可能.
- 量子化学计算提供了对氧原子转移能量的替代效应的见解.
结论:
- 在 [2 + 2] 循环添加中,氧离子是的反应伙伴,产生独特的1,2-氧离子.
- 这些异环是构建更复杂的含环系统的多功能前体.
- 这项研究扩展了有机化学和主要组元素转换的合成工具箱.
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