Palladium-catalysed asymmetric regioselective hydroamination of dienoates†

Bao-Xin Liu , Xin-Ting Qin , Shi-Cun Li , Lei Zhu , Qin Ouyang , Wei Du , Ying-Chun Chen
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Abstract

Electron-deficient dienoates are occasionally utilised in hydrofunctionalisation reactions, and regioselectivity is a common concern. Here we report the palladium-catalysed enantioselective formal 1,4-Michael addition of pyrazoles to δ-aryl-substituted dienoates, proceeding through Pd0 π-Lewis base-mediated protonation followed by regioselective asymmetric amination of the resultant π-allylpalladium species. Moreover, an intramolecular 1,5-addition-type reaction is realised under identical conditions by using δ-aryl-functionalised dienoates, affording indoline products enantioselectively.

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钯催化的脂酸酯不对称区域选择性氢胺化反应
缺电子二烯酸盐偶尔用于氢化反应,区域选择性是一个普遍关注的问题。本文报道了钯催化的吡唑在δ-芳基取代的二烯酸酯上的对映选择性形式1,4- michael加成,其过程是Pd0 π-Lewis碱介导的质子化,然后是合成的π-烯基钯的区域选择性不对称胺化。此外,在相同的条件下,通过δ芳基功能化己烯酸盐实现了分子内1,5加成型反应,使吲哚产物具有对映选择性。
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