通过生成的三氟甲氧基盐实现羧酸的脱氧氟化反应。
Deoxyfluorination of Carboxylic Acids via an Generated Trifluoromethoxide Salt.
作者信息
Lisboa Al Vicente Riano D, Duran-Camacho Geraldo, Ehrlacher Annika K, Lasky Matthew R, Sanford Melanie S
机构信息
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
出版信息
Org Lett. 2023 Dec 22;25(50):9025-9029. doi: 10.1021/acs.orglett.3c03706. Epub 2023 Dec 8.
Abstract
An generated pyridinium trifluoromethoxide salt (PyOCF) is a highly effective deoxyfluorination reagent for the synthesis of acid fluorides. PyOCF is formed at room temperature from the reaction of 2,4-dinitro(trifluoromethoxy)benzene with 4-dimethylaminopyridine. PyOCF undergoes slow release of fluorophosgene and fluoride, which serve as the electrophile and nucleophile, respectively, for deoxyfluorination. A wide substrate scope and high functional group tolerance are demonstrated. Furthermore, the acid fluorides can be purified by filtration and telescoped to various known reactions.
摘要
生成的三氟甲氧基吡啶盐（PyOCF）是一种用于合成酰氟的高效脱氧氟化试剂。PyOCF在室温下由2,4-二硝基（三氟甲氧基）苯与4-二甲氨基吡啶反应形成。PyOCF会缓慢释放出光气氟和氟化物，它们分别作为脱氧氟化反应中的亲电试剂和亲核试剂。该反应展示了广泛的底物范围和高官能团耐受性。此外，酰氟可以通过过滤进行纯化，并可直接应用于各种已知反应。
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Org Lett. 2022 Aug 19;24(32):5962-5966. doi: 10.1021/acs.orglett.2c02232. Epub 2022 Aug 5.
2
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Chemistry. 2022 Aug 1;28(43):e202201589. doi: 10.1002/chem.202201589. Epub 2022 Jun 29.
3
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Chemistry. 2021 Nov 17;27(64):15986-15991. doi: 10.1002/chem.202102809. Epub 2021 Oct 4.
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