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氟代脱羧反应在三氟甲基芳基醚合成中的应用。

Fluorodecarboxylation for the Synthesis of Trifluoromethyl Aryl Ethers.

机构信息

Department of Chemistry, University of California, Berkeley, CA, 94720, USA.

Pfizer Inc., Medicinal Sciences, Groton, CT, 06340, USA.

出版信息

Angew Chem Int Ed Engl. 2016 Aug 8;55(33):9758-62. doi: 10.1002/anie.201604793. Epub 2016 Jul 7.

Abstract

The synthesis of mono-, di-, and trifluoromethyl aryl ethers by fluorodecarboxylation of the corresponding carboxylic acids is reported. AgF2 induces decarboxylation of aryloxydifluoroacetic acids, and AgF, either generated in situ or added separately, serves as a source of fluorine to generate the fluorodecarboxylation products. The addition of 2,6-difluoropyridine increased the reactivity of AgF2 , thereby increasing the range of functional groups and electronic properties of the aryl groups that are tolerated. The reaction conditions used for the formation of trifluoromethyl aryl ethers also served to form difluoromethyl and monofluoromethyl aryl ethers.

摘要

本文报道了通过相应羧酸的脱羧氟化反应合成单、二和三氟甲基芳基醚。AgF2引发芳氧基二氟乙酸的脱羧反应,而原位生成或单独添加的 AgF 则作为氟源生成脱羧氟化产物。添加 2,6-二氟吡啶增加了 AgF2的反应活性,从而扩大了芳基的官能团和电子性质的容忍范围。用于形成三氟甲基芳基醚的反应条件也适用于形成二氟甲基和一氟甲基芳基醚。

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