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镍 NN-钳形配合物介导的脂肪族羧酰胺的合成及对碳同位素标记的适应性。

Synthesis of Aliphatic Carboxamides Mediated by Nickel NN -Pincer Complexes and Adaptation to Carbon-Isotope Labeling.

机构信息

Carbon Dioxide Activation Center (CADIAC), Department of Chemistry and the Interdisciplinary Nanoscience Center (iNANO), Aarhus University., Gustav Wieds Vej 14, 8000, Aarhus C, Denmark.

出版信息

Chemistry. 2018 Oct 9;24(56):14946-14949. doi: 10.1002/chem.201804077. Epub 2018 Sep 11.

DOI:10.1002/chem.201804077
PMID:30106491
Abstract

The development of a nickel-mediated aminocarbonylation utilizing NN -pincer Ni-complexes, alkylzinc reagents, stoichiometric carbon monoxide and amines is described for the first time, which can be adapted to late-stage carbon-isotope labeling. This work expands the scope of the highly established palladium-promoted version of the reaction, by allowing carbon-sp fragments to take part in the three-component reaction. Finally, the results obtained show a remarkable effect of the pincer ligand for the reductive elimination step with the amine, which is followed by C NMR spectroscopy studies.

摘要

首次描述了一种镍介导的氨基羰基化反应,利用 NN-钳形镍配合物、烷基锌试剂、化学计量的一氧化碳和胺,可适应后期的碳同位素标记。这项工作扩展了高度成熟的钯促进版本反应的范围,允许碳片段参与三组分反应。最后,得到的结果表明,胺的还原消除步骤中钳形配体具有显著的效果,随后进行了 C NMR 光谱研究。

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可见光促进的与等当量一氧化碳的未活化碘代烷基的氨甲酰化反应,用于后期阶段的碳同位素标记。
J Org Chem. 2019 Dec 20;84(24):16076-16085. doi: 10.1021/acs.joc.9b02575. Epub 2019 Dec 11.