Use of (E,E)-Dienoic Acids as Switchable (E,E)- and (Z,E)-Dienyl Anion Surrogates via Ligand-Controlled Palladium Catalysis.
Use of (E,E)-Dienoic Acids as Switchable (E,E)- and (Z,E)-Dienyl Anion Surrogates via Ligand-Controlled Palladium Catalysis.
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DOI：
10.1021/jacs.2c10004
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发表时间：
2022-12
影响因子：
15
通讯作者：
Shun-Zhong Tan;Peng-Qiao Chen;Lei Zhu;Meng-Qi Gan;Qin Ouyang;Wei Du;Yingchun Chen
中科院分区：
文献类型：
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作者：
Shun-Zhong Tan;Peng-Qiao Chen;Lei Zhu;Meng-Qi Gan;Qin Ouyang;Wei Du;Yingchun Chen
由于其固有的酸性基团，羧酸不易用作碳基亲核试剂。在这里，我们证明游离的(E,E)-2,4-二烯酸与Pd(0)形成电子中性且占据最高的分子轨道提升的η2-配合物，并以独特的α-区域选择性对亚胺进行弗里德-克来福特型加成，脱羧后得到正式的二烯化产物。分别通过配体控制的外球或内球反应模式实现了不寻常且可切换的（E，E）-和（Z，E）-选择性以及出色的对映选择性，这得到了全面的密度泛函理论计算研究的充分支持。 (E,E)-二烯酸和亚胺之间前所未有的正式还原曼尼希反应也被开发来提供对映体富集的β-氨基酸衍生物。
Carboxylic acids are not readily applied as carbon-based nucleophiles due to their intrinsic acidic group. Here, we demonstrate that free (E,E)-2,4-dienoic acids form electron-neutral and highest occupied molecular orbital-raised η2-complexes with Pd(0) and undergo Friedel-Crafts-type additions to imines with exclusive α-regioselectivity, giving formal dienylated products after decarboxylation. Unusual and switchable (E,E)- and (Z,E)-selectivity, along with excellent enantioselectivity, is achieved via ligand-controlled outer-sphere or inner-sphere reaction modes, respectively, which are well supported by comprehensive density functional theory calculation studies. An unprecedented formal reductive Mannich reaction between (E,E)-dienoic acids and imines is also developed to furnish enantioenriched β-amino acid derivatives.