Chiral Arylated Amines via C-N Coupling of Chiral Amines with Aryl Bromides Promoted by Light
Chiral Arylated Amines via C-N Coupling of Chiral Amines with Aryl Bromides Promoted by Light
复制标题
光促进手性胺与芳基溴的 C-N 偶联形成手性芳基化胺
DOI：
10.1002/anie.202108587
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Dong Xue
中科院分区：
文献类型：
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作者：
Geyang Song;Liu Yang;Jing-Sheng Li;Wei-Jun Tang;Wei Zhang;Rui Cao;Chao Wang;Jianliang Xiao;Dong Xue
Buchwald-Hartwig C-N偶联反应在有机合成中有着广泛的应用。在过去的二十年左右，已经引入了许多改进的催化剂，使得各种胺和芳基亲电试剂现在很容易使用。然而，缺乏可用于偶联宽范围的手性胺和芳基卤化物而不侵蚀对映体过量（ee）的方案。本文报道了一种基于光驱动的分子Ni催化的方法，该方法能够使光学活性胺、氨基醇和氨基酸酯与芳基溴进行立体保留C-N偶联，而不需要任何外部光敏剂。该方法对各种各样的偶联配偶体有效，包括那些带有对碱和亲核试剂敏感的官能团的偶联配偶体，从而为获得合成重要的手性N-芳基胺、氨基醇和氨基酸酯提供了可行的替代方案。92个实例证明了其可行性，ee高达99%。
The Buchwald‐Hartwig C‐N coupling reaction has found widespread applications in organic synthesis. Over the past two decades or so, many improved catalysts have been introduced, allowing various amines and aryl electrophiles to be readily used nowadays. However, there lacks a protocol that could be used to couple a wide range of chiral amines and aryl halides, without erosion of the enantiomeric excess (ee). Reported in this article is a method based on molecular Ni catalysis driven by light, which enables stereoretentive C‐N coupling of optically active amines, amino alcohols, and amino acid esters with aryl bromides, with no need for any external photosensitizer. The method is effective for a wide variety of coupling partners, including those bearing functional groups sensitive to bases and nucleophiles, thus providing a viable alternative to accessing synthetically important chiralN‐aryl amines, amino alcohols, and amino acids esters. Its viability is demonstrated by 92 examples with up to 99 %ee.