钌催化烷基芳酮氨氢直接不对称还原胺化反应

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Joan Gallardo-Donaire, Marko Hermsen, Jedrzej Wysocki, Martin Ernst, Frank Rominger, Oliver Trapp, A. Stephen K. Hashmi, Ansgar Schäfer, Peter Comba, Thomas Schaub*
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引用次数: 76

摘要

介绍了钌催化氨和氢合成伯胺的不对称还原胺化反应。在这里,我们展示了我们的催化剂在使用简单的氨气作为试剂时进行化学和对映选择性过程的能力,氨气是最有吸引力和工业上相关的氮源之一。催化量的碘化铵的存在对于获得良好的产率和对映选择性是必不可少的。通过DFT研究了该反应的机理,发现了一条可行的途径,也解释了卤化物系列对映体选择性的趋势和幅度,与实验数据吻合良好。在反应过程中对底物构象的深入研究是准确预测对映体选择性的关键。此外,我们报告了手性[Ru(I)H(CO)((S,S)-f-binaphane)(PPh3)]配合物的晶体学数据,我们认为这是我们研究中最有效的催化剂。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Direct Asymmetric Ruthenium-Catalyzed Reductive Amination of Alkyl–Aryl Ketones with Ammonia and Hydrogen

Direct Asymmetric Ruthenium-Catalyzed Reductive Amination of Alkyl–Aryl Ketones with Ammonia and Hydrogen

The asymmetric ruthenium-catalyzed reductive amination employing ammonia and hydrogen to primary amines is described. Here we demonstrate the capability of our catalyst to perform a chemo- and enantioselective process while using simple ammonia gas as a reagent, one of the most attractive and industrially relevant nitrogen sources. The presence of a catalytic amount of ammonium iodide was essential for obtaining good yields and enantioselectivities. The mechanism of this reaction was investigated by DFT and we found a viable pathway that also explains the trend and magnitude of enantioselectivity through the halide series in good agreement with the experimental data. The in-depth investigation of substrate conformers during the reaction turned out to be crucial in obtaining an accurate prediction of the enantioselectivity. Furthermore, we report the crystallographic data of the chiral [Ru(I)H(CO)((S,S)-f-binaphane)(PPh3)] complex, which we identified as the most efficient catalyst in our investigation.

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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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