One-Pot Synthesis of Diazirines and 15N2-Diazirines from Ketones, Aldehydes and Derivatives: Development and Mechanistic Insight,Advanced Synthesis & Catalysis

当前位置： X-MOL 学术 › Adv. Synth. Catal. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

One-Pot Synthesis of Diazirines and 15N2-Diazirines from Ketones, Aldehydes and Derivatives: Development and Mechanistic Insight
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2021-07-21 , DOI: 10.1002/adsc.202100679
Quentin Ibert ₁ , Madeleine Cauwel ₂ , Thomas Glachet ₁ , Tony Tite ₃ , patricia Le Nahenec-Martel ₄ , Jean-Francois Lohier ₅ , pierre-yves renard ₆ , Xavier Franck ₂ , Vincent Reboul ₇ , Cyrille Sabot ₃

Affiliation

Broad scope one-pot diazirine synthesis strategies have been developed using two different oxidants depending on the nature of the starting material. In all cases, an inexpensive commercial solution of ammonia (NH₃) in methanol (MeOH) was employed, avoiding the difficult use of liquid ammonia. With aliphatic ketones, t-butyl hypochlorite (t-BuOCl) was found to be the best oxidant whereas it is preferable to use phenyliodine diacetate (PIDA) with aromatic ketones, aldehydes and imines. The nature of the imine-protecting group is essential and only t-butyl imine allowed the synthesis of ¹⁵N₂-diazirine with complete ¹⁵N incorporation, emphasizing a key trans-imination step in the reaction mechanism. These methods are operationally simple, and tolerant to most functional groups, providing diazirines with yields ranging from 20 to 99%.

中文翻译：

从酮、醛和衍生物中一锅法合成二氮丙啶和 15N2-二氮丙啶：发展和机理洞察

根据起始材料的性质，使用两种不同的氧化剂开发了广泛的一锅二氮嗪合成策略。在所有情况下，均采用廉价的商业氨 (NH ₃ ) 甲醇 (MeOH) 溶液，避免了使用液氨的困难。对于脂肪族酮，发现次氯酸叔丁酯 ( t- BuOCl) 是最好的氧化剂，而最好使用带有芳香族酮、醛和亚胺的二乙酸苯碘酯 (PIDA)。亚胺保护基团的性质是必不可少的，只有叔丁基亚胺允许合成¹⁵ N _{2 -二}氮杂环和完整的¹⁵N 掺入，强调反应机制中的关键转亚胺化步骤。这些方法操作简单，对大多数官能团都具有耐受性，提供了产率在 20% 到 99% 之间的二氮嗪。

更新日期：2021-09-21

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11