钴催化苯甲酰胺与含氟炔烃的C-H活化/环化反应：一条合成3-和4-氟烷基异喹啉酮的途径。
Cobalt-Catalyzed C-H Activation/Annulation of Benzamides with Fluorine-Containing Alkynes: A Route to 3- and 4-Fluoroalkylated Isoquinolinones.
作者信息
Kumon Tatsuya, Wu Jianyan, Shimada Miroku, Yamada Shigeyuki, Agou Tomohiro, Fukumoto Hiroki, Kubota Toshio, Hammond Gerald B, Konno Tsutomu
机构信息
Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan.
Department of Materials Science, Ibaraki University, 4-12-1 Nakanarusawa, Hitachi 316-8511, Japan.
出版信息
J Org Chem. 2021 Apr 2;86(7):5183-5196. doi: 10.1021/acs.joc.1c00080. Epub 2021 Mar 16.
Abstract
The C-H activation/annulation reaction of various benzamides with fluoroalkylated alkynes in the presence of a Co(acac)·2HO catalyst proceeded very smoothly to give the corresponding 3- and 4-fluoroalkylated isoquinolinones in excellent yields with approximately 70% regioselectivities. These regioisomers could be successfully separated and obtained in pure form. Major or minor regioisomers were determined as 4- or 3-fluoroalkylated isoquinolinones, respectively, based on X-ray crystallographic analyses.
摘要
在Co(acac)·2H₂O催化剂存在下，各种苯甲酰胺与氟烷基化炔烃的C-H活化/环化反应进行得非常顺利，以优异的产率和大约70%的区域选择性得到相应的3-和4-氟烷基化异喹啉酮。这些区域异构体能够成功分离并以纯形式获得。根据X射线晶体学分析，主要或次要区域异构体分别被确定为4-或3-氟烷基化异喹啉酮。
相似文献
1
Cobalt-Catalyzed C-H Activation/Annulation of Benzamides with Fluorine-Containing Alkynes: A Route to 3- and 4-Fluoroalkylated Isoquinolinones.钴催化苯甲酰胺与含氟炔烃的C-H活化/环化反应：一条合成3-和4-氟烷基异喹啉酮的途径。
J Org Chem. 2021 Apr 2;86(7):5183-5196. doi: 10.1021/acs.joc.1c00080. Epub 2021 Mar 16.
2
Regioselective cobalt(II)-catalyzed [2 + 3] cycloaddition reaction of fluoroalkylated alkynes with 2-formylphenylboronic acids: easy access to 2-fluoroalkylated indenols.区域选择性钴（II）催化的氟烷基化炔烃与2-甲酰基苯硼酸的[2 + 3]环加成反应：简便合成2-氟烷基化茚醇
Beilstein J Org Chem. 2020 Sep 4;16:2193-2200. doi: 10.3762/bjoc.16.184. eCollection 2020.
3
Regioselective one-step synthesis of 4-fluoroalkylated isoquinolines via carbopalladation reaction of fluorine-containing alkynes.通过含氟炔烃的碳钯化反应区域选择性一步合成4-氟烷基异喹啉。
J Org Chem. 2005 Nov 25;70(24):10172-4. doi: 10.1021/jo051700v.
4
A facile regiocontrol in the palladium-catalyzed annulation of fluorine-containing internal alkynes with variously substituted 2-iodoanilines: a new regioselective synthesis of 2- or 3-fluoroalkylated indole derivatives.钯催化含氟内炔与各种取代的2-碘苯胺环化反应中的简便区域控制：2-或3-氟烷基化吲哚衍生物的一种新的区域选择性合成方法。
J Org Chem. 2004 Nov 26;69(24):8258-65. doi: 10.1021/jo048872x.
5
Remarkable access to fluoroalkylated trisubstituted alkenes via highly stereoselective cobalt-catalyzed hydrosilylation reaction of fluoroalkylated alkynes.通过氟烷基化炔烃的高度立体选择性钴催化氢化硅烷化反应，可高效合成氟烷基化三取代烯烃。
Org Biomol Chem. 2009 Mar 21;7(6):1167-70. doi: 10.1039/b819476a. Epub 2009 Jan 29.
6
A remarkable regiocontrol in the palladium-catalyzed silylstannylation of fluoroalkylated alkynes--highly regio- and stereoselective synthesis of multi-substituted fluorine-containing alkenes.钯催化氟烷基化炔烃的硅基锡化反应中显著的区域控制--多取代含氟烯烃的高区域和立体选择性合成。
Org Biomol Chem. 2014 Mar 14;12(10):1611-7. doi: 10.1039/c3ob41903g.
7
Rhodium-catalyzed [2+2+2] cycloaddition of various fluorine-containing alkynes--novel synthesis of multi-substituted fluoroalkylated aromatic compounds.铑催化的各种含氟炔烃的[2+2+2]环加成反应——多取代氟烷基化芳族化合物的新合成方法。
Org Biomol Chem. 2010 Apr 7;8(7):1718-24. doi: 10.1039/b926192c. Epub 2010 Feb 22.
8
Practical Synthesis of -Trifluoromethylated Pyridines Based on Regioselective Cobalt-Catalyzed [2+2+2] Cycloaddition using Trifluoromethylated Diynes with Nitriles.基于三氟甲基化二炔与腈的区域选择性钴催化[2+2+2]环加成反应的三氟甲基吡啶的实用合成方法。
Adv Synth Catal. 2021 Mar 29;363(7):1912-1922. doi: 10.1002/adsc.202001433. Epub 2021 Jan 22.
9
Cobalt-Catalyzed Cyclization of N-Methoxy Benzamides with Alkynes using an Internal Oxidant through C-H/N-O Bond Activation.通过C-H/N-O键活化利用内部氧化剂实现钴催化的N-甲氧基苯甲酰胺与炔烃的环化反应
Chemistry. 2016 Apr 18;22(17):5899-903. doi: 10.1002/chem.201600471. Epub 2016 Mar 16.
10
Nickel-catalyzed C-H/N-H annulation of aromatic amides with alkynes in the absence of a specific chelation system.在无特定螯合体系的情况下，镍催化芳族酰胺与炔烃的C-H/N-H环化反应。
Chem Sci. 2017 Sep 1;8(9):6650-6655. doi: 10.1039/c7sc01750b. Epub 2017 Jul 24.
引用本文的文献
1
Cobalt-Catalyzed Cyclization of 2-Bromobenzamides with Carbodiimides: A New Route for the Synthesis of 3-(Imino)isoindolin-1-ones.钴催化 2-溴苯甲酰胺与碳二亚胺的环化反应：合成 3-(亚氨基)异吲哚啉-1-酮的新途径。
Molecules. 2021 Nov 28;26(23):7212. doi: 10.3390/molecules26237212.
2
On the application of 3d metals for C-H activation toward bioactive compounds: The key step for the synthesis of silver bullets.3D金属在用于生物活性化合物的C-H活化方面的应用：合成“银弹”的关键步骤。
Beilstein J Org Chem. 2021 Jul 30;17:1849-1938. doi: 10.3762/bjoc.17.126. eCollection 2021.
本文引用的文献
1
N-Heterocyclic Carbene Complexes in C-H Activation Reactions.N-杂环卡宾配合物在 C-H 活化反应中的应用。
Chem Rev. 2020 Feb 26;120(4):1981-2048. doi: 10.1021/acs.chemrev.9b00634. Epub 2020 Jan 22.
2
Iridium-Catalyzed Regioselective Synthesis of Trifluoromethylated Isocoumarins through Annulation of Benzoic Acids with Trifluoromethylated Alkynes.铱催化苯甲酸与三氟甲基化炔烃环化反应区域选择性合成三氟甲基化异香豆素
Org Lett. 2019 May 3;21(9):3043-3047. doi: 10.1021/acs.orglett.9b00572. Epub 2019 Mar 26.
3
3d Transition Metals for C-H Activation.用于 C-H 活化的 3d 过渡金属。
Chem Rev. 2019 Feb 27;119(4):2192-2452. doi: 10.1021/acs.chemrev.8b00507. Epub 2018 Nov 27.
4
Cobalt-catalyzed cyclization of benzamides with alkynes: a facile route to isoquinolones with hydrogen evolution.钴催化苯甲酰胺与炔烃的环化反应：一种通过氢解生成异喹啉酮的简便方法。
Org Biomol Chem. 2018 Sep 26;16(37):8384-8389. doi: 10.1039/c8ob01924j.
5
C(sp)-H Trifluoromethylation of enamides using TMSCF: access to trifluoromethylated isoindolinones, isoquinolinones, 2-pyridinones and other heterocycles.TMSCF 促进的烯酰胺的 C(sp)-H 三氟甲基化反应：三氟甲基化异吲哚啉酮、异喹啉酮、2-吡啶酮和其他杂环的合成方法。
Chem Commun (Camb). 2018 Sep 18;54(75):10574-10577. doi: 10.1039/c8cc04907f.
6
A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry.指导基团在金属催化 C-H 官能化化学中的应用综述。
Chem Soc Rev. 2018 Aug 28;47(17):6603-6743. doi: 10.1039/c8cs00201k.
7
Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C-H/N-H Activation with Internal Alkynes.电脱除无痕酰肼用于钴催化电化学氧化 C-H/N-H 键活化与内部炔烃反应。
J Am Chem Soc. 2018 Jun 27;140(25):7913-7921. doi: 10.1021/jacs.8b03521. Epub 2018 Jun 13.
8
Fluorine and Fluorinated Motifs in the Design and Application of Bioisosteres for Drug Design.氟原子及含氟基序在药物设计中生物等排体的设计与应用。
J Med Chem. 2018 Jul 26;61(14):5822-5880. doi: 10.1021/acs.jmedchem.7b01788. Epub 2018 Feb 5.
9
Fluorine Effects on Group Migration via a Rhodium(V) Nitrenoid Intermediate.氟原子对通过铑(V)氮宾中间体的基团迁移的影响。
Angew Chem Int Ed Engl. 2017 Nov 20;56(47):14918-14922. doi: 10.1002/anie.201708505. Epub 2017 Oct 9.
10
Cobalt Catalyzed, Regioselective C(sp)-H Activation of Amides with 1,3-Diynes.钴催化的酰胺与 1,3-二炔的区域选择性 C(sp)-H 活化反应。
Org Lett. 2017 Sep 15;19(18):4758-4761. doi: 10.1021/acs.orglett.7b02119. Epub 2017 Aug 28.
Zotero 插件