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室温下氟化物穿梭促进的铂催化炔烃氢氟化反应

Platinum-Catalysed Hydrofluorination of Alkynes at Room Temperature Promoted by a Fluoride Shuttle.

作者信息

He Ouchan, Jameel Froze, Flammang Hannah, Babu Smrithi Suresh, Kaupp Martin, Braun Thomas

机构信息

Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489, Berlin, Germany.

Department of Chemistry, Technische Universität Berlin, Theoretische Chemie/Quantenchemie, Sekr. C7, Straße des 17. Juni 135, 10623, Berlin, Germany.

出版信息

Angew Chem Int Ed Engl. 2025 Sep 8;64(37):e202512181. doi: 10.1002/anie.202512181. Epub 2025 Jul 23.

Abstract

Hydrofluorination of alkynes provides a synthetic route to access fluoroalkenes, a class of compounds with wide applications in chemical research. Herewith, we describe an exceptional hydrofluorination process of alkynes catalysed by Pt(II) complexes at room temperature. Various Pt(II) dichloride complexes bearing chelating phosphines were synthesised and studied towards their catalytic behaviour. Mechanistic investigations suggest the involvement of a dicationic Pt(II) bis(alkyne) species as well as a cationic ß-fluorovinyl Pt(II) complex in the catalytic cycle. Remarkably, the hydrofluorination is enabled by fluorinated anions. The corresponding acids BF, HF as well as PF act as fluoride shuttles to allow for an outer-sphere fluorination of the metal-bound substrate. Detailed DFT analyses for BF show that the hydrofluorination is mediated by complexes between the fluorinated anion and HF. This lowers the hydrofluorination barriers sufficiently to outcompete the simultaneously occurring, more exergonic cyclisation of two coordinated alkynes to a structurally characterised cycloallyl complex. The catalytic system can be applied to a wide substrate scope to generate fluoroalkenes bearing bulky alkyl, aryl and electron withdrawing groups, such as ester and carbonyl substituents.

摘要

炔烃的氢氟化反应为制备氟代烯烃提供了一条合成路线,氟代烯烃是一类在化学研究中有广泛应用的化合物。在此,我们描述了一种由Pt(II)配合物在室温下催化的炔烃的特殊氢氟化过程。合成了各种带有螯合膦的二氯化Pt(II)配合物,并研究了它们的催化行为。机理研究表明,催化循环中涉及二价阳离子Pt(II)双(炔烃)物种以及阳离子β-氟乙烯基Pt(II)配合物。值得注意的是,氢氟化反应是由氟化阴离子引发的。相应的酸BF、HF以及PF充当氟化物穿梭体,以实现金属结合底物的外层氟代反应。对BF的详细密度泛函理论分析表明,氢氟化反应是由氟化阴离子与HF之间的配合物介导的。这充分降低了氢氟化反应的势垒,从而胜过了同时发生的、两个配位炔烃向具有结构特征的环烯丙基配合物的更放能的环化反应。该催化体系可应用于广泛的底物范围,以生成带有庞大烷基、芳基和吸电子基团(如酯基和羰基取代基)的氟代烯烃。

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