叔丁醇钾介导合成 N-杂二芳基的机理研究
Mechanistic insights into the potassium tert-butoxide-mediated synthesis of N-heterobiaryls.
作者信息
Stephens David E, Lakey-Beitia Johant, Burch Jessica E, Arman Hadi D, Larionov Oleg V
机构信息
Department of Chemistry, The University of Texas at San Antonio, San Antonio, TX 78249, USA.
出版信息
Chem Commun (Camb). 2016 Aug 2;52(64):9945-8. doi: 10.1039/c6cc04816a.
Abstract
We report herein that symmetrical and non-symmetrical N-heterobiaryls are produced by a potassium tert-butoxide-mediated dimerization of heterocyclic N-oxides. The reaction is scalable and transition metal-free, and can be carried out under thermal and microwave conditions. Preliminary mechanistic studies point to the involvement of radical anionic intermediates arising from the N-oxide substrates and potassium tert-butoxide.
摘要
我们在此报告，通过叔丁醇钾介导的杂环N-氧化物二聚反应可生成对称和不对称的N-杂二芳基化合物。该反应可扩大规模且无过渡金属参与，并且可以在热条件和微波条件下进行。初步机理研究表明，反应涉及由N-氧化物底物和叔丁醇钾产生的自由基阴离子中间体。
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本文引用的文献
1
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J Am Chem Soc. 2016 Jun 15;138(23):7402-10. doi: 10.1021/jacs.6b03282. Epub 2016 May 26.
2
Recent Advances in the C-H-Functionalization of the Distal Positions in Pyridines and Quinolines.吡啶和喹啉远端位置的C-H官能化研究进展
Tetrahedron. 2015 Nov 18;71(46):8683-8716. doi: 10.1016/j.tet.2015.08.034. Epub 2015 Aug 19.
3
Transition-Metal-Free α-Arylation of Enolizable Aryl Ketones and Mechanistic Evidence for a Radical Process.无过渡金属参与的烯醇化芳基酮的α-芳基化反应及自由基反应机理的证据
Angew Chem Int Ed Engl. 2015 Sep 1;54(36):10587-91. doi: 10.1002/anie.201502332. Epub 2015 Jul 1.
4
Experimental and mechanistic analysis of the palladium-catalyzed oxidative C8-selective C-H homocoupling of quinoline N-oxides.喹啉 N-氧化物的钯催化氧化 C8 选择性 C-H 均偶联反应的实验与机理分析
Chem Commun (Camb). 2015 Jun 11;51(46):9507-10. doi: 10.1039/c5cc02227d.
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9
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Nat Chem. 2014 Sep;6(9):765-73. doi: 10.1038/nchem.2031.
10
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