Photoinduced Olefin Diamination with Alkylamines
Photoinduced Olefin Diamination with Alkylamines
复制标题
DOI：
10.1002/anie.202005652
复制
发表时间：
2020-06-09
影响因子：
16.6
通讯作者：
Leonori, Daniele
中科院分区：
文献类型：
--
作者：
Govaerts, Sebastian;Angelini, Lucrezia;Leonori, Daniele
邻位二胺是有机化学和药物化学中普遍存在的物质。烯烃和胺的直接偶联将是构建这些基序的理想方法。然而，烯烃二胺化仍然是有机合成中的一个长期挑战，特别是当使用两种不同的胺组分时。我们报告了一个一般性的战略，直接和选择性组装的邻位1，2-二胺使用现成的烯烃和胺的积木。这种温和而直接的方法涉及原位形成和光诱导活化N-氯胺，以产生铵自由基，从而实现有效的烯烃氨基氯化。由于所产生的β-氯胺的两亲性，转化成四烷基氮丙啶离子是可能的，因此能够通过用伯胺或仲胺进行区域选择性开环来进行二胺化。该策略将邻二胺的制备从多步序列简化为单一化学转化。
Vicinal diamines are ubiquitous materials in organic and medicinal chemistry. The direct coupling of olefins and amines would be an ideal approach to construct these motifs. However, alkene diamination remains a long-standing challenge in organic synthesis, especially when using two different amine components. We report a general strategy for the direct and selective assembly of vicinal 1,2-diamines using readily available olefin and amine building blocks. This mild and straightforward approach involves in situ formation and photoinduced activation of N-chloroamines to give aminium radicals that enable efficient alkene aminochlorination. Owing to the ambiphilic nature of the beta-chloroamines produced, conversion into tetra-alkyl aziridinium ions was possible, thus enabling diamination by regioselective ring-opening with primary or secondary amines. This strategy streamlines the preparation of vicinal diamines from multistep sequences to a single chemical transformation.