电化学C(sp)–H氟化反应
Electrochemical C(sp)-H Fluorination.
作者信息
Takahira Yusuke, Chen Miao, Kawamata Yu, Mykhailiuk Pavel, Nakamura Hugh, Peters Byron K, Reisberg Solomon H, Li Chao, Chen Longrui, Hoshikawa Tamaki, Shibuguchi Tomoyuki, Baran Phil S
机构信息
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
Enamine Ltd.; Chervonotkatska 78, 02094 Kyiv (Ukraine) and Taras Shevchenko National University of Kyiv; Chemistry Department; Volodymyrska 64, 01601 Kyiv (Ukraine).
出版信息
Synlett. 2019 Jun;30(10):1178-1182. doi: 10.1055/s-0037-1611737. Epub 2019 Mar 1.
Abstract
A simple and robust method for electrochemical alkyl C-H fluorination is presented. Using a simple nitrate additive, a widely available fluorine source (Selectfluor), and carbon-based electrodes, a wide variety of activated and unactivated C-H bonds were converted to their C-F congeners. The scalability of the reaction was also demonstrated with a 100 gram preparation of fluorovaline.
摘要
本文提出了一种简单且稳健的电化学烷基C-H氟化方法。使用一种简单的硝酸盐添加剂、一种广泛可得的氟源（Selectfluor）和碳基电极，多种活化和未活化的C-H键被转化为其C-F同类物。通过制备100克氟缬氨酸也证明了该反应的可扩展性。
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1
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Chem Soc Rev. 2018 Jul 30;47(15):5786-5865. doi: 10.1039/c7cs00619e.
2
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3
Photofluorination of Aliphatic C-H Bonds Promoted by the Phthalimide Group.
Org Lett. 2018 Mar 2;20(5):1367-1370. doi: 10.1021/acs.orglett.8b00133. Epub 2018 Feb 14.
4
Radical fluorination reactions by thermal and photoinduced methods.
Org Biomol Chem. 2017 Dec 6;15(47):9954-9973. doi: 10.1039/c7ob02402a.
5
Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance.
Chem Rev. 2017 Nov 8;117(21):13230-13319. doi: 10.1021/acs.chemrev.7b00397. Epub 2017 Oct 9.
6
Scalable, Electrochemical Oxidation of Unactivated C-H Bonds.
J Am Chem Soc. 2017 Jun 7;139(22):7448-7451. doi: 10.1021/jacs.7b03539. Epub 2017 May 23.
7
F-Fluorination of Unactivated C-H Bonds in Branched Aliphatic Amino Acids: Direct Synthesis of Oncological Positron Emission Tomography Imaging Agents.
J Am Chem Soc. 2017 Mar 15;139(10):3595-3598. doi: 10.1021/jacs.6b11533. Epub 2017 Mar 1.
8
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Angew Chem Int Ed Engl. 2016 Jul 25;55(31):8923-7. doi: 10.1002/anie.201603149. Epub 2016 Jun 20.
9
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Visible light-promoted metal-free sp(3)-C-H fluorination.
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