On the Unique Reactivity of Pd(OAc)(2) with Organic Azides: Expedient Synthesis of Nitriles and Imines.
On the Unique Reactivity of Pd(OAc)(2) with Organic Azides: Expedient Synthesis of Nitriles and Imines.
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DOI：
10.1002/cctc.201300064
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发表时间：
2013-07
期刊：
影响因子：
4.5
通讯作者：
Diez-Gonzalez, Silvia
中科院分区：
文献类型：
--
作者：
Martinez-Sarti, Laura;Diez-Gonzalez, Silvia
有机叠氮化物是公认的多用途化合物，可以作为不同杂环（三唑，三唑啉，四唑等）或其他含氮化合物的前体，如胺（Staudinger还原，Curtius重排）或亚胺（Schmidt重排，aza-Wittig反应）除了普遍存在的铜催化叠氮化物-炔环加成反应外，近年来有机叠氮化物的两种应用引起了合成界的兴趣：1)通过生成亚硝基化合物[3]制备叠氮嘧啶；2)合成腈。我们对后一种应用特别感兴趣，因为氰基在工业中的重要性，以及它作为有机合成物的实用性。传统的氰化方法存在严重的缺陷，如使用剧毒试剂，产生化学量的金属废物，需要恶劣的条件，官能团耐受性差。叠氮化物允许在几种条件下无氰制备无骨架碳链延伸的腈：强化学量氧化剂（如BF3，[5a] 2,3 -二氯- 5,6 -二氰- 1,4 -苯醌（DDQ），[5b， c]或KI/过氧化叔丁基），[5d] CuSO4/二乙酸苯醚，[6]CuI/过氧化叔丁基，[7]或负载型RuÀOH催化剂。[8]早前的一篇报道将钯放在以炔为氢受体的木炭上，其中性条件和范围引起了我们的注意，不仅限于苯腈衍生物的形成[Eq.(1)]。与其他方法相比，该Pd系统需要严格排除水分和氧气，以便在苯或二乙胺中回流发生任何反应。然而，尽管我们做出了努力，我们仍无法重现报告的结果，只获得了< 20%的转化率。考虑到不同的Pd/C催化剂会导致不确定的结果，我们对反应条件进行了优化（表1）我们
Organic azides are well-established as versatile compounds that can act as precursors of different heterocycles (triazoles, triazolines, tetrazoles, etc.) or other nitrogen-containing compounds, such as amines (Staudinger reduction, Curtius rearrangement) or imines (Schmidt rearrangement, aza-Wittig reaction).[1] Besides the ubiquitous copper-catalysed azide–alkyne cycloaddition reaction,[2] two applications of organic azides have recently attracted the interest of the synthetic community: 1) the preparation of aziridines through the generation of nitrenes [3] and 2) the synthesis of nitriles. We were particularly interested in the latter application, owing to the importance of the cyano group in industry,[4] as well as its utility as an organic synthon. Traditional cyanation methods suffer from serious drawbacks, such as the use of highly toxic reagents, the generation of stoichiometric quantities of metal waste, the need for harsh conditions, and poor functional-group tolerance. Azides allow the cyanide-free preparation of nitriles with no elongation of the skeletal carbon chain under several conditions: strong stoichiometric oxidants (such as BF3,[5a] 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ),[5b, c] or KI/tert-butyl hydroperoxide),[5d] CuSO4/phenyliodonium diacetate,[6] CuI/tertbutyl hydroperoxide,[7] or a supported RuÀOH catalyst.[8] An earlier report, which employed palladium on charcoal with an alkyne as a hydrogen acceptor, caught our attention for its neutral conditions and its scope, which was not restricted to the formation of benzonitrile derivatives [Eq.(1)].[9]In contrast to the other methods, this Pd system required the rigorous exclusion of moisture and oxygen for any reaction to take place at reflux in benzene or diethylamine. However, despite our efforts, we could not reproduce the reported results and only conversions of< 20% were obtained. Considering that different Pd/C catalysts can lead to adventitious results, we optimised the reaction conditions (Table1).[10] We
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