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钯催化的杂环化合物一锅法连续合成的最新进展

Recent Advances in Sequentially Pd-Catalyzed One-Pot Syntheses of Heterocycles.

作者信息

Kornet Maryna M, Müller Thomas J J

机构信息

Institut für Organische Chemie und Makromolekulare Chemie, Mathematisch-Naturwissenschaftliche Fakultät, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany.

Laboratory for Biotechnology of Physiologically Active Substances, Faculty of Biology, Zaporizhzhia National University, 66 Universytetska Str., 69600 Zaporizhzhia, Ukraine.

出版信息

Molecules. 2024 Nov 7;29(22):5265. doi: 10.3390/molecules29225265.

DOI:10.3390/molecules29225265
PMID:39598654
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11596252/
Abstract

Sequential Pd-catalyzed one-pot synthetic methodologies have emerged as a powerful and versatile approach in organic synthesis, enabling the construction of complex heterocyclic architectures with high efficiency, selectivity, and atom economy. This review discusses key advancements in multistep, sequentially Pd-catalyzed one-pot processes for accessing heterocyclic derivatives, focusing on classic reactions like Suzuki-Miyaura, Sonogashira, Heck, and hydroamination and extending to specialized techniques such as directed C-H activation. The concatenation of these steps has advanced the scope of one-pot strategies. A section is dedicated to exploring the cooperative use of palladium with other metals, particularly copper, ruthenium, and gold, which has broadened the range of accessible heterocyclic derivatives. Highlighted applications include the synthesis of biologically and pharmaceutically relevant compounds, such as tris(hetero)aryl systems, spiro-oxindoles, and indole derivatives. These one-pot strategies not only streamline synthesis but also align with green chemistry principles by minimizing purification steps and reducing waste and energy consumption. The review also addresses current challenges and limitations in these methodologies, offering insights into ongoing efforts to optimize reaction conditions and expand the applicability of sequential Pd-catalyzed processes.

摘要

连续钯催化的一锅法合成方法已成为有机合成中一种强大且通用的方法,能够高效、选择性地构建复杂的杂环结构,并具有原子经济性。本文综述了多步连续钯催化一锅法合成杂环衍生物的关键进展,重点讨论了诸如铃木-宫浦反应、园田- Sonogashira反应、Heck反应和氢胺化反应等经典反应,并扩展到如导向C-H活化等专门技术。这些步骤的串联拓展了一锅法策略的范围。其中一部分内容专门探讨了钯与其他金属(特别是铜、钌和金)的协同使用,这拓宽了可获得的杂环衍生物的范围。突出的应用包括生物和药学相关化合物的合成,如三(杂)芳基体系、螺环氧化吲哚和吲哚衍生物。这些一锅法策略不仅简化了合成过程,还通过减少纯化步骤、降低废物和能源消耗符合绿色化学原则。综述还讨论了这些方法当前面临的挑战和局限性,深入探讨了为优化反应条件和扩大连续钯催化过程的适用性而正在进行的努力。

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1
Recent Advances in Sequentially Pd-Catalyzed One-Pot Syntheses of Heterocycles.钯催化的杂环化合物一锅法连续合成的最新进展
Molecules. 2024 Nov 7;29(22):5265. doi: 10.3390/molecules29225265.
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Metal-Catalyzed Approaches toward the Oxindole Core.金属催化的吲哚核心方法。
Acc Chem Res. 2020 Aug 18;53(8):1605-1619. doi: 10.1021/acs.accounts.0c00297. Epub 2020 Jul 24.
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Pd-catalyzed one-pot sequential unsymmetrical cross-coupling reactions of aryl/heteroaryl 1,2-dihalides.钯催化芳基/杂芳基1,2 - 二卤化物的一锅法连续不对称交叉偶联反应
Org Biomol Chem. 2016 Jul 6;14(27):6487-96. doi: 10.1039/c6ob01049k.
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Palladium-Catalyzed One-Pot Approach to 3-(Diarylmethylene)oxindoles from Propiolamidoaryl Triflate.钯催化由炔丙酰胺基芳基三氟甲磺酸酯一锅法合成3-(二芳基亚甲基)氧化吲哚
Molecules. 2015 Aug 3;20(8):14022-32. doi: 10.3390/molecules200814022.
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Pd-catalyzed efficient one-pot sequential cross-coupling reactions of aryl dihalides.钯催化芳基二卤化物的高效一锅法连续交叉偶联反应
Org Lett. 2008 Sep 4;10(17):3849-52. doi: 10.1021/ol801589p. Epub 2008 Aug 6.
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Concatenating Suzuki Arylation and Buchwald-Hartwig Amination by A Sequentially Pd-Catalyzed One-Pot Process-Consecutive Three-Component Synthesis of C,N-Diarylated Heterocycles.通过顺序钯催化的一锅法串联铃木芳基化反应和布赫瓦尔德-哈特维希胺化反应——连续三组分合成C,N-二芳基杂环化合物
Chemistry. 2020 Nov 26;26(66):15130-15134. doi: 10.1002/chem.202003837. Epub 2020 Oct 19.
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Advances in Mechanochemical Methods for One-Pot Multistep Organic Synthesis.一锅多步有机合成的机械化学方法进展
Chemistry. 2025 Jun 17;31(34):e202500798. doi: 10.1002/chem.202500798. Epub 2025 May 24.
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The role of allyl ammonium salts in palladium-catalyzed cascade reactions towards the synthesis of spiro-fused heterocycles.烯丙基铵盐在钯催化的级联反应中合成螺稠合杂环的作用。
Nat Commun. 2020 Oct 23;11(1):5383. doi: 10.1038/s41467-020-19110-3.
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Recent advances in sustainable N-heterocyclic carbene-Pd(II)-pyridine (PEPPSI) catalysts: A review.可持续的氮杂环卡宾-Pd(II)-吡啶(PEPPSI)催化剂的最新进展:综述
Environ Res. 2023 May 15;225:115515. doi: 10.1016/j.envres.2023.115515. Epub 2023 Feb 24.
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Alkynoates as Versatile and Powerful Chemical Tools for the Rapid Assembly of Diverse Heterocycles under Transition-Metal Catalysis: Recent Developments and Challenges.炔酸酯作为在过渡金属催化下快速构建多样杂环的多功能、强效化学工具:最新进展与挑战。
Top Curr Chem (Cham). 2021 Jan 5;379(1):3. doi: 10.1007/s41061-020-00316-4.

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1
Facile One-Pot Fischer-Suzuki-Knoevenagel Microwave-Assisted Synthesis of Fluorescent 5-Aryl-2-Styryl-3-Indoles.简易一锅法微波辅助合成荧光5-芳基-2-苯乙烯基-3-吲哚的费歇尔-铃木-克诺文纳格尔反应
Molecules. 2025 Jun 7;30(12):2503. doi: 10.3390/molecules30122503.
2
Correction: Kornet, M.M.; Müller, T.J.J. Recent Advances in Sequentially Pd-Catalyzed One-Pot Syntheses of Heterocycles. 2024, , 5265.更正:科尔内特,M.M.;米勒,T.J.J. 钯催化的杂环化合物一锅法连续合成的最新进展。2024年,,5265。
Molecules. 2025 Apr 22;30(9):1862. doi: 10.3390/molecules30091862.

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1
Novel meriolin derivatives potently inhibit cell cycle progression and transcription in leukemia and lymphoma cells via inhibition of cyclin-dependent kinases (CDKs).新型meriolin衍生物通过抑制细胞周期蛋白依赖性激酶(CDK),有效抑制白血病和淋巴瘤细胞的细胞周期进程和转录。
Cell Death Discov. 2024 Jun 11;10(1):279. doi: 10.1038/s41420-024-02056-6.
2
Synthesis of Bisindole Alkaloids and Their Mode of Action against Methicillin-Resistant .双吲哚生物碱的合成及其对耐甲氧西林金黄色葡萄球菌的作用模式。
ACS Infect Dis. 2024 Jun 14;10(6):1958-1969. doi: 10.1021/acsinfecdis.3c00657. Epub 2024 Jun 6.
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Novel meriolin derivatives activate the mitochondrial apoptosis pathway in the presence of antiapoptotic Bcl-2.
新型灭绦灵衍生物在抗凋亡蛋白Bcl-2存在的情况下激活线粒体凋亡途径。
Cell Death Discov. 2024 Mar 9;10(1):125. doi: 10.1038/s41420-024-01901-y.
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Palladium(0) π-Lewis Base Catalysis: Concept and Development.零价钯π-路易斯碱催化:概念与发展
J Am Chem Soc. 2024 Mar 13;146(10):6422-6437. doi: 10.1021/jacs.3c14674. Epub 2024 Mar 1.
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Pd-Catalyzed Sequential Electrophilic Cyclization/Selective C-H Annulation Cascade: Synthesis of Isoxazole-Phthalimide-Fused Poly-Heterocyclics.钯催化的顺序亲电环化/选择性C-H环化串联反应:异恶唑-邻苯二甲酰亚胺稠合多杂环化合物的合成
J Org Chem. 2024 Mar 1;89(5):3214-3225. doi: 10.1021/acs.joc.3c02680. Epub 2024 Feb 21.
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Metal-catalyzed coupling/carbonylative cyclizations for accessing dibenzodiazepinones: an expedient route to clozapine and other drugs.用于合成二苯并二氮杂䓬酮的金属催化偶联/羰基化环化反应:一种合成氯氮平和其他药物的便捷途径。
Beilstein J Org Chem. 2024 Jan 31;20:193-204. doi: 10.3762/bjoc.20.19. eCollection 2024.
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A Rational Design of Electrochemically and Photophysically Tunable Triarylamine Luminophores by Consecutive (Pseudo-)Four-Component Syntheses.通过连续(伪)四组分合成法对电化学和光物理性质可调的三芳基胺发光体进行合理设计。
Chemistry. 2024 Mar 20;30(17):e202304119. doi: 10.1002/chem.202304119. Epub 2024 Feb 1.
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Rapid Assembly of Unsymmetrically Linked Bis-heterocycles via Palladium Domino Catalysis.通过钯多米诺催化快速组装不对称连接的双杂环化合物。
Org Lett. 2023 Dec 22;25(50):9053-9057. doi: 10.1021/acs.orglett.3c03825. Epub 2023 Dec 12.
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Palladium-Catalyzed Synthesis of Linked Bis-Heterocycles─Synthesis and Investigation of Photophysical Properties.钯催化的连接双杂环化合物的合成——光物理性质的合成与研究
J Am Chem Soc. 2023 Dec 13;145(49):26623-26631. doi: 10.1021/jacs.3c07234. Epub 2023 Dec 1.
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Gold and Palladium Relay Catalytic [4 + 4] Cycloadditions of Enynamides and γ-Methylene-δ-valerolactones: Diastereoselective Construction of Furan-Fused Azacyclooctanes.烯炔酰胺与γ-亚甲基-δ-戊内酯的金和钯接力催化[4 + 4]环加成反应:呋喃并氮杂环辛烷的非对映选择性构建
J Org Chem. 2023 Aug 18;88(16):11822-11833. doi: 10.1021/acs.joc.3c01114. Epub 2023 Aug 3.