Sirignano Marco, D'Amato Assunta, Costabile Chiara, Mariconda Annaluisa, Crispini Alessandra, Scarpelli Francesca, Longo Pasquale
Department of Chemistry and Biology "A. Zambelli", University of Salerno, Fisciano, Italy.
Department of Science, University of Basilicata, Potenza, Italy.
Front Chem. 2023 Dec 6;11:1260726. doi: 10.3389/fchem.2023.1260726. eCollection 2023.
Imines are valuable key compounds for synthesizing several nitrogen-containing molecules used in biological and industrial fields. They have been obtained, as highly regioselective Markovnikov products, by reacting several alkynes with arylamines in the presence of three new N-Heterocyclic carbene gold(I) complexes (, and ) together with the known and gold complexes as well as silver complexes . Gold(I) complexes were investigated by means of NMR, mass spectroscopy, elemental analysis, and X-ray crystallographic studies. Accurate screening of co-catalysts and solvents led to identifying the best reaction conditions and the most active catalyst () in the model hydroamination of phenylacetylene with aniline. Complex was then tested in the hydroamination of alkynes with a wide variety of arylamines yielding a lower percentage of product when arylamines with both electron-withdrawing and electron-donating substituents were involved. Computational studies on the rate-determining step of hydroamination were conducted to shed light on the significantly different yields observed when reacting arylamines with different substituents.
亚胺是合成生物和工业领域中多种含氮分子的重要关键化合物。通过使几种炔烃与芳胺在三种新型N - 杂环卡宾金（I）配合物（、和）以及已知的和金配合物以及银配合物存在下反应，它们作为高度区域选择性的马氏产物而得到。通过核磁共振、质谱、元素分析和X射线晶体学研究对金（I）配合物进行了研究。对共催化剂和溶剂的精确筛选导致确定了苯乙炔与苯胺的模型加氢胺化反应中的最佳反应条件和最具活性的催化剂（）。然后在炔烃与多种芳胺的加氢胺化反应中测试了配合物，当涉及具有吸电子和供电子取代基的芳胺时，产物的百分率较低。对加氢胺化反应的速率决定步骤进行了计算研究，以阐明当与不同取代基的芳胺反应时观察到的显著不同的产率。
