羰基化锌促进饱和杂环中的亚甲基插入：机理认识和反应性剖析

Synthesis Pub Date : 2024-07-16 DOI:10.1055/s-0043-1775381

Hiroyuki Nakamura, Masato Tsuda

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摘要

本文介绍了利用类羰基锌通过亚甲基插入 N-O 键使饱和杂环扩环的方法。1,2-oxazetidines 和 1,2-oxazolidines 可应用这种转化，而 N-对甲苯磺酸化的 1,2-oxazinane 则可生成开环产物。密度泛函理论计算表明了环扩张的逐步反应机制，并阐明了所观察到的不同反应活性的起源。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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Zinc Carbenoid-Promoted Methylene Insertion in Saturated Heterocycles: Mechanistic Insights and Reactivity Profiles

The ring expansion of saturated heterocycles through methylene insertion into N–O bonds using a zinc carbenoid is described. This transformation is applied to 1,2-oxazetidines and 1,2-oxazolidines, while N-tosylated 1,2-oxazinane affords a ring-opened product. Density functional theory calculations suggest a stepwise reaction mechanism of the ring expansion and elucidate the origins of the different reactivities observed.

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Synthesis

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