Organometallic Ru(III) Catalysts for α-Alkylation of Carbonyl Compounds using Alcohols: Mechanistic Insights via Detection of Key Intermediates.

IF 3.5 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - An Asian Journal Pub Date : 2024-11-01 DOI:10.1002/asia.202400811

Sain Singh, Rajat Saini, Virendra Kumar Chaudhary, Kaushik Ghosh

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引用次数: 0

Abstract

Three novel cyclometalated ruthenium complexes ([Ru.L(9)] [Ru.L(10)] and [Ru.L(11)]) featuring azo functionalities were synthesized and characterized using a variety of spectroscopic techniques, namely FT-IR, electronic absorption spectroscopy, and ESI-MS. Representative solid-state structures of the acquired complexes were determined through X-ray crystallography. These complexes were evidenced to be efficient catalysts for the synthesis of various α-alkylated compounds utilizing simple acetophenone derivatives with easily affordable and economically viable alcohols, which were isolated and characterized via 1H and 13C NMR spectroscopy. The optimum reaction conditions were found by employing toluene as solvent, potassium tert-butoxide as base at 115 oC temperature utilizing 0.8 mol% of catalyst [Ru.L(10)]. The yield of the desired compounds found to be in the range of 83 - 97%. Additionally, mass spectrometry provided insights into the in-situ generated ruthenium hydride and ruthenium alkoxy intermediates, shedding light on the catalytic mechanism.

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使用醇对羰基化合物进行 α-烷基化反应的有机金属 Ru(III) 催化剂：通过检测关键中间体揭示机理。

本研究合成了三种具有偶氮官能团的新型环甲基化钌配合物（[Ru.L(9)] [Ru.L(10)] 和 [Ru.L(11)]），并利用多种光谱技术（即傅立叶变换红外光谱、电子吸收光谱和 ESI-MS）对其进行了表征。通过 X 射线晶体学确定了所获得复合物的代表性固态结构。研究证明，这些复合物是利用简单的苯乙酮衍生物和价格低廉、经济可行的醇合成各种 α 烷基化化合物的高效催化剂，并通过 1H 和 13C NMR 光谱对这些化合物进行了分离和表征。以甲苯为溶剂，叔丁醇钾为碱，温度为 115 oC，催化剂[Ru.L(10)]为 0.8 摩尔%，找到了最佳反应条件。结果发现，所需化合物的产率在 83 - 97% 之间。此外，质谱分析还揭示了原位生成的氢化钌和烷氧基钌中间体，从而揭示了催化机理。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemistry - An Asian Journal 化学-化学综合

CiteScore

7.00

自引率

2.40%

发文量

535

审稿时长

1.3 months

期刊介绍： Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics. Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews. A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal. Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).