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甲酸盐介导的芳基/乙烯基卤化物与三氟甲磺酸盐的C-C偶联:羰基芳基化和还原交叉偶联

Formate-Mediated C-C Coupling of Aryl/Vinyl Halides and Triflates: Carbonyl Arylation and Reductive Cross-Coupling.

作者信息

Chang Yu-Hsiang, Cho Yoon, Shen Weijia, Krische Michael J

机构信息

University of Texas at Austin, Department of Chemistry Welch Hall (A5300), 105 E 24th St., Austin, TX 78712, USA.

出版信息

ACS Catal. 2025 May 16;15(10):8274-8283. doi: 10.1021/acscatal.5c01994. Epub 2025 May 2.

DOI:10.1021/acscatal.5c01994
PMID:40843079
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12366644/
Abstract

Catalytic methods for the intermolecular formate-mediated C-C coupling of Csp-X pronucleophiles beyond reductive Heck reactions (alkene hydroarylations) are catalogued. These methods include transfer hydrogenative reductive couplings of aryl/vinyl halides or triflates to carbonyl compounds (Grignard/NHK-type reactions), as well as reductive cross-couplings of two aryl/vinyl halide or triflate partners. These studies demonstrate that reactions traditionally associated with discrete Csp carbanions can be rendered catalytic and free from premetalated reagents or metallic reductants using sodium or potassium formate - abundant, low molecular weight sources of hydrogen.

摘要

除还原Heck反应(烯烃氢芳基化)外,用于Csp-X亲核前体分子间甲酸介导的C-C偶联的催化方法已被分类。这些方法包括芳基/乙烯基卤化物或三氟甲磺酸酯与羰基化合物的转移氢化还原偶联(格氏/NHK型反应),以及两个芳基/乙烯基卤化物或三氟甲磺酸酯底物的还原交叉偶联。这些研究表明,传统上与离散的Csp碳负离子相关的反应可以使用甲酸钠或甲酸钾(丰富、低分子量的氢源)实现催化,且无需预金属化试剂或金属还原剂。

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本文引用的文献

1
Aryl halide cross-coupling via formate-mediated transfer hydrogenation.通过甲酸盐介导的转移氢化实现芳基卤化物交叉偶联。
Nat Chem. 2025 May;17(5):710-718. doi: 10.1038/s41557-024-01729-0. Epub 2025 Mar 11.
2
Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis.交叉亲电偶联:合成中的原理、方法及应用
Chem Rev. 2024 Dec 11;124(23):13397-13569. doi: 10.1021/acs.chemrev.4c00524. Epub 2024 Nov 26.
3
Formate-Mediated Reductive Cross-Coupling of Vinyl Halides and Aryl Iodides: -Substitution via Palladium(I) Catalysis.
卤代乙烯和芳基碘化物的甲酸介导还原交叉偶联:通过钯(I)催化的α-取代反应
Org Lett. 2024 Aug 23;26(33):7055-7059. doi: 10.1021/acs.orglett.4c02642. Epub 2024 Aug 12.
4
Intermolecular Metal-Catalyzed C‒C Coupling of Unactivated Alcohols or Aldehydes for Convergent Ketone Construction beyond Premetalated Reagents.分子间金属催化未活化醇或醛的C-C偶联反应用于构建超越预金属化试剂的收敛性酮类化合物。
ACS Catal. 2023 Aug 18;13(16):10976-10987. doi: 10.1021/acscatal.3c02209. Epub 2023 Aug 4.
5
Pd(0)-Catalyzed Asymmetric Intramolecular Grignard-Type Reaction of Vinyl Iodide-Carbonyl.钯(0)催化的乙烯基碘-羰基的不对称分子内格氏型反应
Chemistry. 2024 May 2;30(25):e202400236. doi: 10.1002/chem.202400236. Epub 2024 Mar 13.
6
Palladium-Catalyzed Electrooxidative Double C-H Arylation.钯催化的电氧化双C-H芳基化反应
J Am Chem Soc. 2024 Jan 10;146(1):228-239. doi: 10.1021/jacs.3c08479. Epub 2023 Dec 27.
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Palladium(I)-Iodide-Catalyzed Deoxygenative Heck Reaction of Vinyl Triflates: A Formate-Mediated Cross-Electrophile Reductive Coupling with -Substitution.钯(I)-碘催化的乙烯基三氟甲磺酸酯的脱氧Heck反应:一种由甲酸介导的具有β-取代的交叉亲电体还原偶联反应。
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