NiH-Catalyzed Remote Asymmetric Hydroalkylation of Alkenes with Racemic -Bromo Amides
NiH-Catalyzed Remote Asymmetric Hydroalkylation of Alkenes with Racemic -Bromo Amides
复制标题
NiH 催化的烯烃与外消旋溴酰胺的远程不对称加氢烷基化
DOI：
10.1002/anie.201813222
复制
发表时间：
2019-02-04
影响因子：
16.6
通讯作者：
Zhu, Shaolin
中科院分区：
文献类型：
--
作者：
Zhou, Fang;Zhang, Yao;Zhu, Shaolin
报道了烯烃与外消旋溴代酰胺的末端选择性远程不对称加氢烷基化反应。该反应通过NiH催化的烯烃异构化和随后的烷基化反应进行，并且可以将来自外消旋-溴酰胺的不对称仲烷基对映会聚地引入到沿着烯烃的烃链的末端C（sp（3））-H位置上。这种温和的方法以优异的产率和高的区域选择性和对映选择性提供了一系列结构多样的手性烷基烷酰胺。此外，通过异构烯烃混合物的工业原料大规模区域收敛转化为对映体化的-烷基链烷酰胺，进一步突出了该方案的合成效用。
Reported here is a terminal-selective, remote asymmetric hydroalkylation of olefins with racemic -bromo amides. The reaction proceeds by NiH-catalyzed alkene isomerization and subsequent alkylation reaction, and can enantioconvergently introduce an unsymmetrical secondary alkyl group from a racemic -bromo amide onto a terminal C(sp(3))-H position along the hydrocarbon chain of the alkene. This mild process affords a range of structurally diverse chiral -alkylalkanoic amides in excellent yields, and high regio- and enantioselectivities. In addition, the synthetic utility of this protocol is further highlighted by the regioconvergent conversion of industrial raw materials of isomeric olefin mixtures into enantioriched -alkylalkanoic amides on large scale.