Hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins.
Hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins.
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DOI：
10.1021/ja062355
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发表时间：
2006-08
影响因子：
15
通讯作者：
J. Waser;B. Gášpár;H. Nambu;E. Carreira
中科院分区：
文献类型：
--
作者：
J. Waser;B. Gášpár;H. Nambu;E. Carreira
报道了钴、锰催化烯烃氢化肼化和氢化叠氮化反应的发现、研究和实施。这些反应等同于C-C双键与受保护的肼或叠氮酸的直接氢化胺化，但基于不同的概念，其中H和N原子来自两种不同的试剂，硅烷和氧化氮源（偶氮二羧酸酯或磺酰叠氮）。使用偶氮二羧酸二叔丁酯的氢化肼化反应的特征在于其易于使用、大官能团耐受性和宽范围，包括单-、二-、三-和四取代烯烃。该反应的发展关键在于磺酰叠氮化合物作为氮源的使用和叔丁基过氧化氢的活化作用。该反应被发现是有效的单，二，和三取代的烯烃的官能化，只有少数官能团是不容许的。得到的烷基叠氮化合物是多用途的中间体，并且可以在不分离叠氮化合物的情况下转化为游离胺或三唑。初步的机理研究表明，限速氢钴的烯烃，然后由胺化反应。不能排除自由基中间体，可能涉及。
The discovery, study, and implementation of the Co- and Mn-catalyzed hydrohydrazination and hydroazidation reactions of olefins are reported. These reactions are equivalent to direct hydroaminations of C-C double bonds with protected hydrazines or hydrazoic acid but are based on a different concept in which the H and the N atoms come from two different reagents, a silane and an oxidizing nitrogen source (azodicarboxylate or sulfonyl azide). The hydrohydrazination reaction using di-tert-butyl azodicarboxylate is characterized by its ease of use, large functional group tolerance, and broad scope, including mono-, di-, tri-, and tetrasubstituted olefins. Key to the development of the hydroazidation reaction was the use of sulfonyl azides as nitrogen sources and the activating effect of tert-butyl hydroperoxide. The reaction was found to be efficient for the functionalization of mono-, di-, and trisubstituted olefins, and only a few functional groups are not tolerated. The alkyl azides obtained are versatile intermediates and can be transformed to the free amines or triazoles without isolation of the azides. Preliminary mechanistic investigations suggest a rate-limiting hydrocobaltation of the alkene, followed by an amination reaction. Radical intermediates cannot be ruled out and may be involved.