通过β-C(sp)-H活化实现（杂）芳基碘化物与酮的多功能烷基化反应。
Versatile Alkylation of (Hetero)Aryl Iodides with Ketones via β-C(sp)-H Activation.
作者信息
Zhu Ru-Yi, Liu Luo-Yan, Park Han Seul, Hong Kai, Wu Yongwei, Senanayake Chris H, Yu Jin-Quan
机构信息
Department of Chemistry, The Scripps Research Institute , La Jolla, California 92037, United States.
Department of Chemical Development, Boehringer Ingelheim Pharmaceuticals Inc. , Ridgefield, Connecticut 06877, United States.
出版信息
J Am Chem Soc. 2017 Nov 15;139(45):16080-16083. doi: 10.1021/jacs.7b09761. Epub 2017 Nov 3.
Abstract
We report Pd(II)-catalyzed β-C(sp)-H (hetero)arylation of a variety of ketones using a commercially available 2,2-dimethyl aminooxyacetic acid auxiliary. Facile installation and removal of the auxiliary as well as its superior scope for both ketones and (hetero)aryl iodides overcome the significant limitations of the previously reported β-C(sp)-H arylation of ketones. The ready availability of ketones renders this reaction a broadly useful method for alkyl-(hetero)aryl coupling involving both primary and secondary alkyls.
摘要
我们报道了使用市售的2,2-二甲基氨基氧基乙酸助剂，钯（II）催化多种酮的β-C（sp）-H（杂）芳基化反应。该助剂的轻松安装和去除，以及其对酮和（杂）芳基碘化物的优异适用范围，克服了先前报道的酮的β-C（sp）-H芳基化反应的重大局限性。酮的容易获得使该反应成为涉及伯烷基和仲烷基的烷基-（杂）芳基偶联的广泛有用的方法。
相似文献
1
Versatile Alkylation of (Hetero)Aryl Iodides with Ketones via β-C(sp)-H Activation.通过β-C(sp)-H活化实现（杂）芳基碘化物与酮的多功能烷基化反应。
J Am Chem Soc. 2017 Nov 15;139(45):16080-16083. doi: 10.1021/jacs.7b09761. Epub 2017 Nov 3.
2
Palladium-catalyzed oxidative coupling of trialkylamines with aryl iodides leading to alkyl aryl ketones.钯催化的三烷基胺与芳基碘的氧化偶联反应生成芳基烷基酮。
Org Lett. 2011 May 6;13(9):2184-7. doi: 10.1021/ol200404z. Epub 2011 Apr 7.
3
An efficient process for pd-catalyzed C-N cross-coupling reactions of aryl iodides: insight into controlling factors.一种用于芳基碘化物的钯催化C-N交叉偶联反应的高效方法：对控制因素的洞察
J Am Chem Soc. 2009 Apr 29;131(16):5766-8. doi: 10.1021/ja901414u.
4
Mild, Aqueous α-Arylation of Ketones: Towards New Diversification Tools for Halogenated Metabolites and Drug Molecules.酮的温和水相α-芳基化反应：迈向卤代代谢物和药物分子的新型多样化工具
Chemistry. 2017 Mar 17;23(16):3832-3836. doi: 10.1002/chem.201700680. Epub 2017 Mar 6.
5
Direct synthesis of aryl ketones by palladium-catalyzed desulfinative addition of sodium sulfinates to nitriles.钯催化亚磺酸钠对腈的脱亚磺酰加成直接合成芳基酮。
Chemistry. 2011 Jul 11;17(29):7996-9. doi: 10.1002/chem.201101252. Epub 2011 May 30.
6
Atmospheric pressure aminocarbonylation of aryl iodides using palladium nanoparticles supported on MOF-5.使用负载在 MOF-5 上的钯纳米粒子实现芳基碘代物的常压氨基羰基化反应。
Chem Commun (Camb). 2012 Feb 7;48(12):1805-7. doi: 10.1039/c2cc16808a.
7
Pd-catalyzed copper-free carbonylative Sonogashira reaction of aryl iodides with alkynes for the synthesis of alkynyl ketones and flavones by using water as a solvent.钯催化的芳基碘化物与炔烃的无铜羰基化Sonogashira反应，以水为溶剂合成炔基酮和黄酮。
J Org Chem. 2005 Jul 22;70(15):6097-100. doi: 10.1021/jo050498t.
8
Palladium-Catalyzed Pyrazole-Directed sp C-H Bond Arylation for the Synthesis of β-Phenethylamines.钯催化吡唑导向的 sp3 C-H 键芳基化反应合成 β-苯乙胺。
Angew Chem Int Ed Engl. 2017 Mar 20;56(13):3630-3634. doi: 10.1002/anie.201611407. Epub 2017 Feb 24.
9
Copper-catalyzed direct synthesis of diaryl 1,2-diketones from aryl iodides and propiolic acids.铜催化由芳基碘化物和丙炔酸直接合成二芳基1,2 - 二酮
J Org Chem. 2014 Jul 3;79(13):6279-85. doi: 10.1021/jo501089k. Epub 2014 Jun 24.
10
Pd/Cu-catalyzed C-H arylation of 1,3,4-thiadiazoles with (hetero)aryl iodides, bromides, and triflates.Pd/Cu 催化的 1,3,4-噻二唑与（杂）芳基碘代物、溴代物和三氟甲磺酸酯的 C-H 芳基化反应。
J Org Chem. 2012 Oct 5;77(19):8768-74. doi: 10.1021/jo301401q. Epub 2012 Sep 21.
引用本文的文献
1
Exercise in 1-aryl-3-CF-1-pyrazoles: regioselective synthesis of 4-/5-iodides and cross-coupling reactions.1-芳基-3-三氟甲基-1-吡唑类化合物的反应：4-/5-碘化物的区域选择性合成及交叉偶联反应
RSC Adv. 2025 Mar 25;15(12):9225-9229. doi: 10.1039/d5ra01103e. eCollection 2025 Mar 21.
2
β-C-H bond functionalization of ketones and esters by cationic Pd complexes.阳离子钯配合物对酮和酯的β-C-H键官能团化反应
Nature. 2025 Jan;637(8046):608-614. doi: 10.1038/s41586-024-08281-4. Epub 2025 Jan 8.
3
Iodoarene-directed photoredox β-C(sp)-H arylation of 1-(-iodoaryl)alkan-1-ones with cyanoarenes halogen atom transfer and hydrogen atom transfer.碘芳烃导向的1-（碘芳基）烷-1-酮与氰基芳烃的光氧化还原β-C（sp）-H芳基化反应——卤素原子转移和氢原子转移
Chem Sci. 2024 Mar 26;15(17):6522-6529. doi: 10.1039/d3sc06637a. eCollection 2024 May 1.
4
Pd-Catalyzed -C(sp)-H (Hetero)Arylation of Ketones Enabled by Transient Directing Groups.瞬态导向基团实现的钯催化酮的-C(sp)-H（杂）芳基化反应
ACS Catal. 2022 Sep 2;12(17):10581-10586. doi: 10.1021/acscatal.2c03400. Epub 2022 Aug 15.
5
Transition-Metal-Catalyzed C-H Bond Activation for the Formation of C-C Bonds in Complex Molecules.过渡金属催化的 C-H 键活化在复杂分子中 C-C 键的形成。
Chem Rev. 2023 Jun 28;123(12):7692-7760. doi: 10.1021/acs.chemrev.2c00888. Epub 2023 May 10.
6
β- and γ-C(sp )-H Heteroarylation of Free Carboxylic Acids: A Modular Synthetic Platform for Diverse Quaternary Carbon Centers.β- 和 γ-C(sp )-H 杂芳基化游离羧酸：用于多样季碳原子的模块化合成平台。
Angew Chem Int Ed Engl. 2023 Feb 20;62(9):e202214459. doi: 10.1002/anie.202214459. Epub 2023 Jan 24.
7
Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp)-H Bonds.过渡金属催化的非活化 C(sp3)-H 键的配位辅助功能化。
Chem Rev. 2021 Dec 22;121(24):14957-15074. doi: 10.1021/acs.chemrev.1c00519. Epub 2021 Oct 29.
8
Hexafluoroisopropanol: the magical solvent for Pd-catalyzed C-H activation.六氟异丙醇：钯催化C-H活化的神奇溶剂。
Chem Sci. 2021 Feb 10;12(11):3857-3870. doi: 10.1039/d0sc06937j.
9
Merging C(sp)-H activation with DNA-encoding.将C(sp) -H活化与DNA编码相结合。
Chem Sci. 2020 Sep 7;11(45):12282-12288. doi: 10.1039/d0sc03935g.
10
Distal γ-C(sp )-H Olefination of Ketone Derivatives and Free Carboxylic Acids.酮衍生物和游离羧酸的远端γ-C(sp )-H 烯烃化反应。
Angew Chem Int Ed Engl. 2020 Jul 27;59(31):12853-12859. doi: 10.1002/anie.202003271. Epub 2020 Jun 5.
本文引用的文献
1
-Arylation of oxime ethers using diaryliodonium salts through activation of inert C(sp)-H bonds using a palladium catalyst.通过钯催化剂活化惰性C(sp)-H键，使用二芳基碘鎓盐对肟醚进行芳基化反应。
Chem Sci. 2016 Feb 1;7(2):1383-1387. doi: 10.1039/c5sc03903g. Epub 2015 Nov 11.
2
Methylene C(sp)-H Arylation of Aliphatic Ketones Using a Transient Directing Group.使用瞬态导向基团实现脂肪族酮的亚甲基C(sp)-H芳基化反应
ACS Catal. 2017 Oct 6;7(10):6938-6941. doi: 10.1021/acscatal.7b02905. Epub 2017 Sep 13.
3
Highly Versatile β-C(sp)-H Iodination of Ketones Using a Practical Auxiliary.实用助剂促进酮的高立体选择性β-C(sp3)-H 碘化反应。
J Am Chem Soc. 2017 Sep 13;139(36):12394-12397. doi: 10.1021/jacs.7b06851. Epub 2017 Aug 29.
4
Synthesis of α-santonin derivatives for diminutive effect on T and B-cell proliferation and their structure activity relationships.用于对T和B细胞增殖产生微小影响的α-山道年衍生物的合成及其构效关系。
Eur J Med Chem. 2017 Feb 15;127:1047-1058. doi: 10.1016/j.ejmech.2016.11.018. Epub 2016 Nov 9.
5
Catalytic C-H Arylation of Aliphatic Aldehydes Enabled by a Transient Ligand.瞬变配体促进的脂肪族醛的催化 C-H 芳基化反应
J Am Chem Soc. 2016 Oct 5;138(39):12775-12778. doi: 10.1021/jacs.6b08478. Epub 2016 Sep 26.
6
Single-Electron Transmetalation via Photoredox/Nickel Dual Catalysis: Unlocking a New Paradigm for sp(3)-sp(2) Cross-Coupling.单电子转移的光氧化还原/镍双催化：为 sp(3)-sp(2)交叉偶联开辟新范式。
Acc Chem Res. 2016 Jul 19;49(7):1429-39. doi: 10.1021/acs.accounts.6b00214. Epub 2016 Jul 5.
7
Organic chemistry. Functionalization of C(sp3)-H bonds using a transient directing group.有机化学。使用瞬态导向基团对C(sp3)-H键进行官能团化。
Science. 2016 Jan 15;351(6270):252-6. doi: 10.1126/science.aad7893.
8
Iridium(III)-catalyzed direct arylation of C-H bonds with diaryliodonium salts.铱(III)催化的芳基碘盐与 C-H 键的直接芳基化反应。
J Am Chem Soc. 2015 Sep 30;137(38):12231-40. doi: 10.1021/jacs.5b06758. Epub 2015 Sep 22.
9
Enantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C-C Bonds.用于构建碳-碳键的有机金属试剂的对映选择性和对映特异性过渡金属催化交叉偶联反应。
Chem Rev. 2015 Sep 9;115(17):9587-652. doi: 10.1021/acs.chemrev.5b00162. Epub 2015 Aug 13.
10
Analysis of the structural diversity, substitution patterns, and frequency of nitrogen heterocycles among U.S. FDA approved pharmaceuticals.分析美国 FDA 批准的药物中氮杂环的结构多样性、取代模式和频率。
J Med Chem. 2014 Dec 26;57(24):10257-74. doi: 10.1021/jm501100b. Epub 2014 Oct 7.
Zotero 插件