-氨基吡啶叶立德导向、铜促进的sp C-H键胺化反应
-Aminopyridinium Ylide-Directed, Copper-Promoted Amination of sp C-H Bonds.
作者信息
Kwak Se Hun, Daugulis Olafs
机构信息
Department of Chemistry , University of Houston , Houston , Texas 77204-5003 , United States.
出版信息
J Org Chem. 2019 Oct 18;84(20):13022-13032. doi: 10.1021/acs.joc.9b01847. Epub 2019 Sep 10.
Abstract
-Aminopyridinium ylides are used as monodentate directing groups for copper-promoted C-H/N-H coupling of sp C-H bonds with pyrazoles, imidazoles, and sulfonamides. Reactions proceed in fluorinated alcohol solvents at elevated temperatures and require use of 1.3-3 equiv of copper(II) acetate. This appears to be the first method for copper-promoted C-H/N-H coupling directed by a removable monodentate auxiliary in absence of added ligands.
摘要
-氨基吡啶叶立德用作单齿导向基团，用于铜促进的sp C-H键与吡唑、咪唑和磺酰胺的C-H/N-H偶联反应。反应在氟化醇溶剂中于高温下进行，需要使用1.3 - 3当量的醋酸铜(II)。这似乎是在不添加配体的情况下，由可去除的单齿助剂导向的铜促进的C-H/N-H偶联反应的第一种方法。
相似文献
1
-Aminopyridinium Ylide-Directed, Copper-Promoted Amination of sp C-H Bonds.
J Org Chem. 2019 Oct 18;84(20):13022-13032. doi: 10.1021/acs.joc.9b01847. Epub 2019 Sep 10.
2
-Aminopyridinium Ylide-Directed, Copper-Promoted Chalcogenation of Arene C-H Bonds.
J Org Chem. 2020 Oct 16;85(20):13069-13079. doi: 10.1021/acs.joc.0c01757. Epub 2020 Oct 1.
3
1-Aminopyridinium Ylides as Monodentate Directing Groups for sp C-H Bond Functionalization.
J Am Chem Soc. 2019 Sep 18;141(37):14728-14735. doi: 10.1021/jacs.9b06643. Epub 2019 Sep 6.
4
N-Iminopyridinium ylide-directed, cobalt-catalysed coupling of sp C-H bonds with alkynes.
Chem Commun (Camb). 2020 Sep 22;56(75):11070-11073. doi: 10.1039/d0cc05294a.
5
Direct functionalization processes: a journey from palladium to copper to iron to nickel to metal-free coupling reactions.
Acc Chem Res. 2013 Feb 19;46(2):412-24. doi: 10.1021/ar300185z. Epub 2012 Oct 26.
6
Bidentate, monoanionic auxiliary-directed functionalization of carbon-hydrogen bonds.
Acc Chem Res. 2015 Apr 21;48(4):1053-64. doi: 10.1021/ar5004626. Epub 2015 Mar 10.
7
Unlocking ylide reactivity in the metal-catalyzed allylic substitution reaction: stereospecific construction of primary allylic amines with aza-ylides.
J Am Chem Soc. 2009 Jul 1;131(25):8722-3. doi: 10.1021/ja9041302.
8
A General Method for Aminoquinoline-Directed, Copper-Catalyzed sp(2) C-H Bond Amination.
J Am Chem Soc. 2016 Apr 6;138(13):4601-7. doi: 10.1021/jacs.6b01117. Epub 2016 Mar 18.
9
Use of a readily removable auxiliary group for the synthesis of pyrrolidones by the palladium-catalyzed intramolecular amination of unactivated γ C(sp(3))-H bonds.
Angew Chem Int Ed Engl. 2013 Oct 11;52(42):11124-8. doi: 10.1002/anie.201305615. Epub 2013 Aug 27.
10
Intermolecular Amination of Unactivated C(sp )-H Bonds with Cyclic Alkylamines: Formation of C(sp )-N Bonds through Copper/Oxygen-Mediated C(sp )-H/N-H Activation.
Chemistry. 2016 Nov 2;22(45):16057-16061. doi: 10.1002/chem.201603370. Epub 2016 Sep 29.
引用本文的文献
1
-Amino Pyridinium Salts in Organic Synthesis.
Org Chem Front. 2023 May 21;10(10):2563-2580. doi: 10.1039/d3qo00190c. Epub 2023 Mar 30.
2
-Aminopyridinium Ylide-Directed, Copper-Promoted Chalcogenation of Arene C-H Bonds.
J Org Chem. 2020 Oct 16;85(20):13069-13079. doi: 10.1021/acs.joc.0c01757. Epub 2020 Oct 1.
3
N-Iminopyridinium ylide-directed, cobalt-catalysed coupling of sp C-H bonds with alkynes.
Chem Commun (Camb). 2020 Sep 22;56(75):11070-11073. doi: 10.1039/d0cc05294a.
本文引用的文献
1
1-Aminopyridinium Ylides as Monodentate Directing Groups for sp C-H Bond Functionalization.
J Am Chem Soc. 2019 Sep 18;141(37):14728-14735. doi: 10.1021/jacs.9b06643. Epub 2019 Sep 6.
2
3d Transition Metals for C-H Activation.
Chem Rev. 2019 Feb 27;119(4):2192-2452. doi: 10.1021/acs.chemrev.8b00507. Epub 2018 Nov 27.
3
Nickel-Catalyzed Electrooxidative C-H Amination: Support for Nickel(IV).
Chemistry. 2018 Dec 20;24(72):19166-19170. doi: 10.1002/chem.201805441. Epub 2018 Nov 21.
4
Copper-Mediated Amination of Aryl C-H Bonds with the Direct Use of Aqueous Ammonia via a Disproportionation Pathway.
J Am Chem Soc. 2018 Oct 31;140(43):14350-14356. doi: 10.1021/jacs.8b08826. Epub 2018 Oct 22.
5
2,4-Diamino-1,3,5-triazine-enabled Cu-catalyzed direct sulfonamidation of aromatic C-H bonds.
Org Biomol Chem. 2017 Aug 30;15(34):7212-7217. doi: 10.1039/c7ob01872j.
6
Dibenzothiophene Sulfoximine as an NH Surrogate in the Synthesis of Primary Amines by Copper-Catalyzed C-X and C-H Bond Amination.
Angew Chem Int Ed Engl. 2017 Aug 1;56(32):9532-9535. doi: 10.1002/anie.201705025. Epub 2017 Jul 5.
7
Identification of monodentate oxazoline as a ligand for copper-promoted -C-H hydroxylation and amination.
Chem Sci. 2017 Feb 1;8(2):1469-1473. doi: 10.1039/c6sc03383k. Epub 2016 Sep 26.
8
Ligand-Promoted Rhodium(III)-Catalyzed ortho-C-H Amination with Free Amines.
Angew Chem Int Ed Engl. 2017 Jun 19;56(26):7449-7453. doi: 10.1002/anie.201703300. Epub 2017 May 29.
9
Copper(II)-Mediated Chelation-Assisted Regioselective N-Naphthylation of Indoles, Pyrazoles and Pyrrole through Dehydrogenative Cross-Coupling.
J Org Chem. 2017 May 5;82(9):4883-4890. doi: 10.1021/acs.joc.7b00615. Epub 2017 Apr 25.
10
Transition Metal-Catalyzed C-H Amination: Scope, Mechanism, and Applications.
Chem Rev. 2017 Jul 12;117(13):9247-9301. doi: 10.1021/acs.chemrev.6b00644. Epub 2017 Jan 4.
Zotero 插件