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氯化锌催化的芳腈格氏加成反应。

Zinc chloride-catalyzed Grignard addition reaction of aromatic nitriles.

作者信息

Hatano Manabu, Kuwano Kisara, Asukai Riho, Nagayoshi Ayako, Hoshihara Haruka, Hirata Tsubasa, Umezawa Miho, Tsubaki Sahori, Yoshikawa Takeshi, Sakata Ken

机构信息

Faculty of Pharmaceutical Sciences, Kobe Pharmaceutical University Higashinada Kobe 658-8558 Japan

Faculty of Pharmaceutical Sciences, Toho University Miyama, Funabashi Chiba 274-8510 Japan

出版信息

Chem Sci. 2024 May 13;15(22):8569-8577. doi: 10.1039/d4sc01659a. eCollection 2024 Jun 5.

DOI:10.1039/d4sc01659a
PMID:38846385
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11151835/
Abstract

In the alkyl addition reaction of aromatic nitriles using Grignard reagents, ketones are formed after hydrolysis. However, this addition reaction is often slow compared to that using reactive organolithium(i) reagents. In this study, we improved the reaction by using zinc(ii)ates, which are generated using Grignard reagents and zinc chloride (ZnCl) as a catalyst. As a result, the corresponding ketones and amines were obtained hydrolysis and reduction, respectively, in good yields under mild reaction conditions. Scale-up reactions are also demonstrated. Interestingly, using a catalytic amount of ZnCl was more effective than using a stoichiometric amount of zinc(ii)ates. Possible transition states are proposed on the basis of the active zinc(ii)ate species, and DFT calculations were carried out to elucidate a plausible reaction mechanism.

摘要

在使用格氏试剂进行芳香腈的烷基加成反应中，水解后会生成酮。然而，与使用活性有机锂（i）试剂的反应相比，这种加成反应通常较慢。在本研究中，我们通过使用由格氏试剂和氯化锌（ZnCl）作为催化剂生成的锌（ii）酸盐改进了反应。结果，在温和的反应条件下，分别通过水解和还原以良好的产率得到了相应的酮和胺。还展示了放大反应。有趣的是，使用催化量的ZnCl比使用化学计量的锌（ii）酸盐更有效。基于活性锌（ii）酸盐物种提出了可能的过渡态，并进行了密度泛函理论（DFT）计算以阐明合理的反应机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc02/11151835/3161acd00098/d4sc01659a-f4.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc02/11151835/e56e0ce381b6/d4sc01659a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc02/11151835/3161acd00098/d4sc01659a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc02/11151835/878596b7ddf9/d4sc01659a-s1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc02/11151835/f50a5faed1b7/d4sc01659a-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc02/11151835/09ae4a760820/d4sc01659a-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc02/11151835/b05273a2e1c5/d4sc01659a-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc02/11151835/3b6023885ff5/d4sc01659a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc02/11151835/db68cbc22743/d4sc01659a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc02/11151835/e56e0ce381b6/d4sc01659a-f3.jpg
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ChemSusChem. 2022 Oct 10;15(19):e202201348. doi: 10.1002/cssc.202201348. Epub 2022 Aug 30.
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The Grignard Reaction - Unraveling a Chemical Puzzle.格氏反应——揭开化学谜题。
J Am Chem Soc. 2020 Feb 12;142(6):2984-2994. doi: 10.1021/jacs.9b11829. Epub 2020 Jan 30.
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Introducing Glycerol as a Sustainable Solvent to Organolithium Chemistry: Ultrafast Chemoselective Addition of Aryllithium Reagents to Nitriles under Air and at Ambient Temperature.
引入甘油作为有机锂化学的可持续溶剂：在空气和环境温度下芳基锂试剂对腈的超快速化学选择性加成。
Chemistry. 2018 Feb 1;24(7):1720-1725. doi: 10.1002/chem.201705577. Epub 2018 Jan 15.
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Unprecedented Nucleophilic Additions of Highly Polar Organometallic Compounds to Imines and Nitriles Using Water as a Non-Innocent Reaction Medium.使用水作为非亲核反应介质的高度极性有机金属化合物对亚胺和腈的前所未有的亲核加成。
Angew Chem Int Ed Engl. 2017 Aug 14;56(34):10200-10203. doi: 10.1002/anie.201705412. Epub 2017 Jul 26.
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