应变驱动的,非催化环扩张的异环
Maximilian P Müller1, Alexander Hinz1
1Karlsruhe Institute of Technology, Institute for Inorganic Chemistry, Engesserstr. 15, 76131, Karlsruhe, Germany.
Chemistry (Weinheim an der Bergstrasse, Germany)
|July 25, 2023
概括
小的环,包括烯和烯,当与异尼烯反应时,很容易扩大成更大的环. 这种反应是由环应变驱动的,在较大的环结构中不太常见.
科学领域:
- 有机化学 有机化学
- 异环化学 异环化学
- 反应机制 反应机制
背景情况:
- 环是合成化学中的多功能构建块.
- 催化膨胀是一种修改轮大小的常见方法.
- 非协调性西利烯及其衍生异环的反应性具有显著的兴趣.
研究的目的:
- 为了研究从无基的士烯中衍生出的小环的环膨胀反应.
- 为了探索环扩展环的后续异构化路径.
- 用计算方法确定这些反应的范围和局限性.
主要方法:
- 从特定的米烯中合成西里兰,西里兰,西里兰,西莱坦和西洛林.
- 非催化环膨胀反应与异.
- 密度函数理论 (DFT) 计算来分析反应机制和预测范围.
主要成果:
- 三个成员的环 (silirane,silirene,phosphasilirene) 经过易于,非催化环扩张与isonitriles形成四个成员的环.
- 环扩张的酸盐通过酶胺形成和随后的环扩张表现出进一步的异构.
- DFT计算证实了对具有异尼的三成员环的普遍环扩张,但对四成员和更大的环的范围有限.
结论:
- 小的,紧张的环很容易发生与异二烯的环膨胀反应.
- 在酸盐中观察到的同质化级联提供了新的合成可能性.
- 环张力是一个关键因素,决定了环膨胀反应的可行性.
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