A general, electrocatalytic approach to the synthesis of vicinal diamines
A general, electrocatalytic approach to the synthesis of vicinal diamines
复制标题
DOI：
10.1038/s41596-018-0010-0
复制
发表时间：
2018-08-01
期刊：
影响因子：
14.8
通讯作者：
Lin, Song
中科院分区：
文献类型：
--
作者：
Fu, Niankai;Sauer, Gregory S.;Lin, Song
该方案描述了由烯烃电化学合成1，2-二叠氮化合物。有机叠氮化物是合成化学、材料和生物应用的高度通用的中间体。1，2-二叠氮化物通常被还原形成1，2-二胺，其是生物活性天然产物、治疗剂和分子催化剂中普遍存在的结构基序。1，2-二叠氮化合物的电化学形成涉及从叠氮化钠阳极生成叠氮基自由基，然后将该N-中心自由基连续两次添加到烯烃中，并且由Mn催化剂辅助。1，2-二叠氮化物的电合成可以使用各种实验装置进行，所述实验装置包括定制的或市售的反应容器和直流电源。可以使用容易获得的电极材料，包括碳（由网状玻璃碳和铅笔芯制成）、镍泡沫和铂箔。该协议也证明了使用ElectraSyn，一个标准化的电化学试剂盒。与传统的合成方法相比，电化学允许精确控制阳极电位输入，消除了对化学计量和通常不加选择的氧化剂的需要，并最大限度地减少了浪费的副产物的产生。因此，我们的电催化合成表现出各种优势，现有的烯烃二胺化的方法，包括可持续性，操作简单，基板的一般性，和特殊的官能团相容性。所得的1，2-二叠氮化合物可以在一个步骤中以高的化学选择性顺利地还原为1，2-二胺。为了证明这一点，我们包括一个程序，催化氢化使用钯碳。因此，该方案构成了从烯烃获得1，2-二叠氮化物和1，2-二胺的一般方法。
This protocol describes an electrochemical synthesis of 1,2-diazides from alkenes. Organic azides are highly versatile intermediates for synthetic chemistry, materials, and biological applications. 1,2-Diazides are commonly reduced to form 1,2-diamines, which are prevalent structural motifs in bioactive natural products, therapeutic agents, and molecular catalysts. The electrochemical formation of 1,2-diazides involves the anodic generation of an azidyl radical from sodium azide, followed by two successive additions of this N-centered radical to the alkene, and is assisted by a Mn catalyst. The electrosynthesis of 1,2-diazides can be carried out using various experimental setups comprising custommade or commercially available reaction vessels and a direct-current power supply. Readily accessible electrode materials can be used, including carbon (made from reticulated vitreous carbon and pencil lead), nickel foam, and platinum foil. This protocol is also demonstrated using ElectraSyn, a standardized electrochemistry kit. Compared with conventional synthetic approaches, electrochemistry allows for the precise control of the anodic potential input, eliminates the need for stoichiometric and often indiscriminate oxidants, and minimizes the generation of wasteful byproducts. As such, our electrocatalytic synthesis exhibits various advantages over existing methods for alkene diamination, including sustainability, operational simplicity, substrate generality, and exceptional functional-group compatibility. The resultant 1,2-diazides can be smoothly reduced to 1,2-diamines in a single step with high chemoselectivity. To exemplify this, we include a procedure for catalytic hydrogenation using palladium on carbon. This protocol, therefore, constitutes a general approach to accessing 1,2-diazides and 1,2-diamines from alkenes.