Ruan Xiao-Yun, Wu Dan-Xing, Li Wen-Ao, Lin Zihan, Sayed Mostafa, Han Zhi-Yong, Gong Liu-Zhu
Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
J Am Chem Soc. 2024 May 1;146(17):12053-12062. doi: 10.1021/jacs.4c01690. Epub 2024 Apr 15.
Three-component diene carboaminations offer a potent means to access synthetically valuable allylic amines with rapid molecular complexity escalation. The existing literature primarily discloses racemic examples, necessitating the use of halides/pseudohalides as substrates. This paper introduces a photoinduced Pd-catalyzed enantioselective three-component carboamination of aryl-substituted 1,3-dienes, leveraging aliphatic C-H bonds for rapid synthesis. The reaction employs 10 mol % of chiral palladium catalyst and an excess aryl bromide as the HAT reagent. This approach yields diverse chiral allylamines with moderate to excellent enantioselectivities. Notably, it stands as the first instance of an asymmetric three-component diene carboamination reaction, directly utilizing abundant C(sp)-H bearing partners, such as toluene-type substrates, ethers, amines, esters, and ketones. The protocol exhibits versatility across amines, encompassing aliphatic, aromatic, primary, and secondary derivatives. This method could serve as a versatile platform for stereoselective incorporation of various nucleophiles, dienes, and C(sp)-H bearing partners.
三组分二烯碳胺化反应提供了一种有效的方法，能够快速增加分子复杂性，从而获得具有合成价值的烯丙基胺。现有文献主要报道的是外消旋的例子，需要使用卤化物/拟卤化物作为底物。本文介绍了一种光诱导钯催化的芳基取代1,3 - 二烯的对映选择性三组分碳胺化反应，利用脂肪族C - H键实现快速合成。该反应使用10 mol%的手性钯催化剂和过量的芳基溴作为氢原子转移（HAT）试剂。这种方法能够以中等至优异的对映选择性生成多种手性烯丙基胺。值得注意的是，这是首例不对称三组分二烯碳胺化反应，直接利用了大量含C(sp³)-H的底物，如甲苯类底物、醚、胺、酯和酮。该方案在胺类底物方面具有通用性，包括脂肪族、芳香族、伯胺和仲胺衍生物。这种方法可以作为一个通用平台，用于立体选择性地引入各种亲核试剂、二烯和含C(sp³)-H的底物。
