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Synlett 2024; 35(03): 347-351
DOI: 10.1055/a-2122-8406
DOI: 10.1055/a-2122-8406
cluster
Organic Chemistry Under Visible Light: Photolytic and Photocatalytic Organic Transformations
Photoredox Defluorinative Silylation of α-Trifluoromethyl Arylalkenes Using Silacarboxylic Acids as Silyl Radical Precursors
We acknowledge financial support from the National Natural Science Foundation of China (21961006, 22071036, 32172459), National Basic Research Program of China (2022YFD1700300), The 10 Talent Plan (Shicengci) of Guizhou Province ([2016]5649), the Science and Technology Department of Guizhou Province ([2019]1020, Qiankehejichu-ZK[2021]Key033), the Program of Introducing Talents of Discipline to Universities of China (111 Program, D20023) at Guizhou University, Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules, Department of Education, Guizhou Province [Qianjiaohe KY (2020)004], and Guizhou University (China).
Abstract
A photoredox defluorinative silylation of α-trifluoromethyl arylalkenes for rapid access to useful gem-difluoroalkenes is disclosed. Stable and easily prepared silacarboxylic acids are used as silyl radical precursors in a photocatalytic decarboxylative process. The mild conditions and operational simplicity make our method a straightforward strategy to construct gem-difluoroalkenes bearing various functional groups, and a powerful strategy for incorporating a gem-difluoroalkene moiety into natural products and drug molecules.
Key words
photoredox reaction - defluorination - silylation - difluoroalkenes - silyl radicals - late-stage modificationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2122-8406.
- Supporting Information
Publication History
Received: 26 May 2023
Accepted after revision: 04 July 2023
Accepted Manuscript online:
04 July 2023
Article published online:
21 August 2023
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- 16 Silylated gem-Difluoroalkenes 3a–z; General Procedure A screw-capped vial equipped with a stirrer bar was charged with the appropriate silanecarboxylic acid 1 (0.1 mmol, 1.0 equiv), difluoroalkene 2 (0.11 mmol, 1.1 equiv), 4CzIPN (PC1 ; 2 mol%), and K2CO3 (0.15 mmol, 1.5 equiv) under N2 in a glove box. EtOAc (1.5 mL) was added the vial from a syringe, and the vial was sealed with a cap containing a PTFE septum and removed from the glove box. The stirred mixture was then irradiated by a 20 W blue LED under a N2 balloon for 12 h. When the reaction was complete, the crude mixture was purified by flash chromatography (silica gel, PE). (3,3-Difluoro-2-phenylprop-2-en-1-yl)(dimethyl)phenylsilane (3a)17 Colourless oil; yield: 27 mg (93%). 1H NMR (400 MHz, CDCl3): δ = 7.41–7.44 (m, 2 H), 7.20–7.35 (m, 8 H,), 1.98 (dd, J = 2.1 Hz, J= 3.1 Hz, 2 H), 0.15 (s, 6 H). 13C NMR (101 MHz, CDCl3): δ = 152.7 (dd, J = 284.3 Hz, J = 288.1 Hz), 138.2, 134.9 (dd, J = 3.7 Hz, J = 5.1 Hz), 133.4, 129.1, 128.3 (t, J = 2.9 Hz), 128.2, 127.7, 127.1, 90.0 (dd, J = 14.6 Hz, 23.4 Hz), 16.5, –3.0. 19F NMR (377 MHz, CDCl3): δ = –91.7 (d, J = 48.6 Hz), –94.3 (d, J = 48.5 Hz).
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