Switching from 2-pyridination to difluoromethylation: ligand-enabled nickel-catalyzed reductive difluoromethylation of aryl iodides with difluoromethyl 2-pyridyl sulfone

IF 10.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Science China Chemistry Pub Date : 2023-09-18 DOI:10.1007/s11426-023-1791-3

Wei Du, Qinyu Luo, Zhiqiang Wei, Xiu Wang, Chuanfa Ni, Jinbo Hu

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Abstract

The divergent reductive cross-coupling with an ambident electrophile is rare. Previously, we demonstrated a nickel-catalyzed reductive 2-pyridination of aryl iodides with difluoromethyl 2-pyridyl sulfone (2-PySO₂CF₂H) via selective C(sp²)–S bond cleavage of the sulfone by using a phosphine ligand. In this communication, we report a novel nickel-catalyzed reductive coupling of aryl iodides and 2-PySO₂CF₂H reagent, which constitutes a new method for aromatic difluoromethylation. The use of a tridentate terpyridine ligand is pivotal for the selective C(sp³)–S bond cleavage of the sulfone. This method employs readily available nickel catalyst and 2-PySO₂CF₂H as the difluoromethylation reagent, providing a facile access to difluoromethylarenes under mild reaction conditions without pre-generation of arylmetal reagents.

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从2-吡啶化转变为二氟甲基化：配体使能的镍催化二氟甲基-2-吡啶砜还原二氟甲基芳基碘化物

与双稳态亲电试剂的发散还原交叉偶联是罕见的。此前，我们证明了镍催化的芳基碘化物与二氟甲基2-吡啶基砜（2-PySO2CF2H）的还原2-吡啶化，通过使用膦配体选择性切割砜的C（sp2）–S键。在这篇通讯中，我们报道了一种新的芳基碘化物和2-PySO2CF2H试剂的镍催化还原偶联，这构成了一种芳香族二氟甲基化的新方法。三齿三联吡啶配体的使用对于砜的选择性C（sp3）–S键断裂至关重要。该方法使用易得的镍催化剂和2-PySO2CF2H作为二氟甲基化试剂，在温和的反应条件下提供了容易获得二氟甲基芳烃的途径，而无需预生成芳基金属试剂。

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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.