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铜（I）催化的乌尔曼-戈德堡C-N偶联反应中高催化剂负载量的起源

Origins of high catalyst loading in copper(i)-catalysed Ullmann-Goldberg C-N coupling reactions.

作者信息

Sherborne Grant J, Adomeit Sven, Menzel Robert, Rabeah Jabor, Brückner Angelika, Fielding Mark R, Willans Charlotte E, Nguyen Bao N

机构信息

Institute of Process Research & Development , School of Chemistry , University of Leeds , Woodhouse Lane , Leeds , LS2 9JT , UK . Email:

Leibniz Institut für Katalyse e.V , Albert-Einstein Straβe 29a , 18059 , Rostock , Germany.

出版信息

Chem Sci. 2017 Oct 1;8(10):7203-7210. doi: 10.1039/c7sc02859h. Epub 2017 Aug 29.

DOI:10.1039/c7sc02859h
PMID:29147546
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5688446/
Abstract

A mechanistic investigation of Ullmann-Goldberg reactions using soluble and partially soluble bases led to the identification of various pathways for catalyst deactivation through (i) product inhibition with amine products, (ii) by-product inhibition with inorganic halide salts, and (iii) ligand exchange by soluble carboxylate bases. The reactions using partially soluble inorganic bases showed variable induction periods, which are responsible for the reproducibility issues in these reactions. Surprisingly, more finely milled CsCO resulted in a longer induction period due to the higher concentration of the deprotonated amine/amide, leading to suppressed catalytic activity. These results have significant implications on future ligand development for the Ullmann-Goldberg reaction and on the solid form of the inorganic base as an important variable with mechanistic ramifications in many catalytic reactions.

摘要

使用可溶性碱和部分可溶性碱对乌尔曼-戈德堡反应进行的机理研究，确定了催化剂失活的各种途径，包括：（i）胺产物的产物抑制；（ii）无机卤化物盐的副产物抑制；以及（iii）可溶性羧酸盐碱的配体交换。使用部分可溶性无机碱的反应表现出可变的诱导期，这是这些反应中重现性问题的原因。令人惊讶的是，研磨得更细的碳酸铯由于去质子化胺/酰胺浓度较高，导致诱导期更长，从而抑制了催化活性。这些结果对未来乌尔曼-戈德堡反应的配体开发以及无机碱的固体形式具有重要意义，无机碱的固体形式是许多催化反应中具有机理影响的重要变量。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/261f/5688446/453ef588467f/c7sc02859h-f5.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/261f/5688446/453ef588467f/c7sc02859h-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/261f/5688446/ab1e5bffb4b9/c7sc02859h-s1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/261f/5688446/453ef588467f/c7sc02859h-f5.jpg

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Angew Chem Int Ed Engl. 1998 Aug 17;37(15):2046-2067. doi: 10.1002/(SICI)1521-3773(19980817)37:15<2046::AID-ANIE2046>3.0.CO;2-L.
2
Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions.钯催化的碳-氮交叉偶联反应的应用
Chem Rev. 2016 Oct 12;116(19):12564-12649. doi: 10.1021/acs.chemrev.6b00512. Epub 2016 Sep 30.
3
Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings.
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Heliyon. 2020 Feb 4;6(2):e03233. doi: 10.1016/j.heliyon.2020.e03233. eCollection 2020 Feb.
Ullmann 型 C-O 和 C-N 偶联中官能团的正交区分。
J Org Chem. 2016 Sep 2;81(17):7315-25. doi: 10.1021/acs.joc.6b01035. Epub 2016 Jun 9.
4
Analysis of Past and Present Synthetic Methodologies on Medicinal Chemistry: Where Have All the New Reactions Gone?药物化学中过去与现在合成方法的分析：新反应都去哪儿了？
J Med Chem. 2016 May 26;59(10):4443-58. doi: 10.1021/acs.jmedchem.5b01409. Epub 2015 Dec 1.
5
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