金(I)通过羟基二氢嗪中间体催化Azinium离子的亲核丙基化反应。

IF 3.7 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - A European Journal Pub Date : 2025-01-13 DOI:10.1002/chem.202404153

Jack Smithson, Luke O'Brien, Kieran D. Jones, Stephen P. Argent, Katherine M. Wheelhouse, Simon Woodward, Kristaps Ermanis, Hon Wai Lam

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引用次数: 0

摘要

在金(I)的催化下，氮离子与丙基硼酸盐的亲核丙基化反应有效进行。一系列n -烷基化的吡啶、喹啉和吡嗪离子经过丙基化，产率高，区域选择性高，得到各种功能化的1,4-二氢吡啶、1,2-二氢吡啶、1,4-二氢喹啉、1,2-二氢喹啉和4,5-二氢吡嗪。未观察到烯丙化副产物。密度泛函理论（DFT）计算提供了深入了解这些反应的机理。在这些反应中，由LiOH与azinium离子加成形成的羟基二氢氮中间体是活性亲电试剂。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Gold(I)-Catalyzed Nucleophilic Propargylation of Azinium Ions via Hydroxydihydroazine Intermediates

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Gold(I)-Catalyzed Nucleophilic Propargylation of Azinium Ions via Hydroxydihydroazine Intermediates

The nucleophilic propargylation of azinium ions with a propargylboronate proceeds efficiently under gold(I) catalysis. A range of N-alkylated pyridinium, quinolinium, and pyrazinium ions undergo propargylation with good yields and high regioselectivities to give various functionalized 1,4-dihydropyridines, 1,2-dihydropyridines, 1,4-dihydroquinolines, 1,2-dihydroquinolines, and 4,5-dihydropyrazines. No allenylation side-products are observed. Density functional theory (DFT) calculations provided insight into the mechanisms of these reactions. Hydroxydihydroazine intermediates formed by the addition of LiOH to the azinium ions were found to be the reactive electrophiles in these reactions.

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来源期刊

Chemistry - A European Journal 化学-化学综合

CiteScore

7.90

自引率

4.70%

发文量

1808

审稿时长

1.8 months

期刊介绍： Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields. Based in Europe Chemistry—A European Journal provides an excellent platform for increasing the visibility of European chemistry as well as for featuring the best research from authors from around the world. All manuscripts are peer-reviewed, and electronic processing ensures accurate reproduction of text and data, plus short publication times. The Concepts section provides nonspecialist readers with a useful conceptual guide to unfamiliar areas and experts with new angles on familiar problems. Chemistry—A European Journal is published on behalf of ChemPubSoc Europe, a group of 16 national chemical societies from within Europe, and supported by the Asian Chemical Editorial Societies. The ChemPubSoc Europe family comprises: Angewandte Chemie, Chemistry—A European Journal, European Journal of Organic Chemistry, European Journal of Inorganic Chemistry, ChemPhysChem, ChemBioChem, ChemMedChem, ChemCatChem, ChemSusChem, ChemPlusChem, ChemElectroChem, and ChemistryOpen.