Mechanistic Studies into Metal-Catalyzed Aldoxime to Amide Rearrangements

Mechanistic Studies into Metal-Catalyzed Aldoxime to Amide Rearrangements
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DOI:
10.1002/adsc.201100650
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发表时间:
2011-12-01
影响因子:
5.4
通讯作者:
Williams, Jonathan M. J.
Williams, Jonathan M. J.
中科院分区:
化学2区
文献类型:
--
作者:
Allen, C. Liana;Lawrence, Ruth;Williams, Jonathan M. J.

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金属催化的醛肟重排合成伯胺是一种完全原子经济的合成方法,可用于制备化学上最重要的官能团之一。已有多种金属成功催化这一反应的报道,然而,对于其中涉及的机理,存在着相互矛盾的观点。在这里,我们报告了新的实验证据来支持这一机制,以及这是否对所有已报道的催化剂都适用,或者是金属特有的。我们还介绍了我们对镍催化胺与醛肟的酰化反应机理的进一步研究。
The metal-catalyzed rearrangement of aldoximes into primary amides is a completely atom economical synthetic method for the preparation of one of the most important functional groups in chemistry. There have been several reports of various metals successfully catalyzing this reaction, however, there are conflicting views as to the mechanism involved. Herein we report new experimental evidence to support the mechanism and whether this is universal to all catalysts reported or metal specific. We also describe our further studies into the mechanism of the nickel-catalyzed acylation of amines with aldoximes.