Ligand-Free Pd-Catalyzed Direct C-H Arylation of Polyfluoroarenes with Aryl Iodides under Ambient Air Conditions.

IF 3.5 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - An Asian Journal Pub Date : 2025-03-12 DOI:10.1002/asia.202500073

Yudha P Budiman, Pambudi A Tasripin, Muhammad R Ramadhan, Raiza Hannifah, Yusi Deawati, Tri Mayanti, Solihudin, Miftahussurur H Putra, Udo Radius, Todd B Marder

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Abstract

We report the synergistic use of Pd(OAc)₂ and Ag₂O for the direct C-H arylation of polyfluoroarenes with aryl iodides in DMF as the solvent. This method is straightforward, can be conducted in air, and does not require additional ligands, yielding fluorinated unsymmetrical biaryl products in up to 99 %. Experimental studies and DFT calculations suggest that the formation of [(DMF)₂Pd^II(C₆F₅)₂] in DMF as a coordinating solvent does not inhibit the reaction, as the Pd complex reacts with aryl iodides by oxidative addition upon dissociation of a single DMF ligand to form [(DMF)Pd^IV(C₆F₅)₂(Ar)(I)] before the desired arylation product is released. This contrasts with our previous report on the nucleophilic coupling between C₆F₅H and aryl-Bpin, in which the formation of [(DMF)₂Pd^II(C₆F₅)₂] was found to halt the reaction.

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环境空气条件下无配体pd催化的多氟芳烃与芳基碘化物直接C-H芳基化反应

我们报道了Pd（OAc）₂和Ag₂O在DMF作为溶剂下与芳基碘化物直接C-H芳化反应的协同作用。这种方法很简单，可以在空气中进行，并且不需要额外的配体，产生氟化不对称联芳基产品的比例高达99%。实验研究和DFT计算表明，在DMF作为配位溶剂中形成[(DMF)2PdII(C6F5)2]并不会抑制反应，因为Pd配合物在单个DMF配体解离后通过氧化加成与芳基碘化物反应，形成[(DMF)PdIV(C6F5)2(Ar)(I)]，然后释放所需的芳基化产物。这与我们之前关于C₆F₅H和芳基bpin之间的亲核偶联的报告形成对比，其中发现[(DMF) 2 PdII（C₆F₅）2]的形成阻止了反应。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemistry - An Asian Journal 化学-化学综合

CiteScore

7.00

自引率

2.40%

发文量

535

审稿时长

1.3 months

期刊介绍： Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics. Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews. A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal. Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).