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Synlett 2024; 35(19): 2241-2245
DOI: 10.1055/s-0043-1763759
DOI: 10.1055/s-0043-1763759
letter
AgSCF3 Radical Addition Based on an Oxidant-Free α,β-Amide (Trifluoromethyl)sulfanylation Reaction
Authors
We are grateful for the financial support from the National Natural Science Foundation of China (GZ-1645), the Key Research & Development Project in Shaanxi Province (2022GY-195, 2023-YBGY-183), the Basic Research Project of Natural Science of Shaanxi Province (2021JLM-30), and Shaanxi Provincial Department of Education Science and Technology Project (23JY028).
Abstract
(Trifluoromethyl)sulfanylamides are an important class of organic compounds that are common among natural products and drug molecules. Here, we report a (trifluoromethyl)sulfanylation reaction using silver(I) (trifluoromethyl)sulfide as a free-radical (trifluoromethyl)sulfanylation reagent for β-amide compounds. This reaction does not require stoichiometric oxidants or additional transition-metal catalysts, and can be achieved by adding common organic acids. This method has excellent applicability and can accommodate several functional groups, including ester groups, acyl groups, and even bromo or iodo groups. Heterocyclic α,β-amides can also be readily converted into the corresponding products. This reaction also provides a new method for the synthesis of deuterated (trifluoromethyl)sulfanylamides.
Key words
(trifluoromethyl)sulfanylation - acid catalyst - amides - free-radical reaction - silver AgSCF3Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/-0043-1763759.
- Supporting Information (PDF) (opens in new window)
Publication History
Received: 17 December 2023
Accepted after revision: 06 March 2024
Article published online:
18 April 2024
© 2024. Thieme. All rights reserved
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- 31 N-Aryl-3-[(trifluoromethyl)sulfanyl]propanamides (3a–al); General Procedure A 35.0 mL glass reaction tube was charged with the appropriate acrylamide 1 (1.0 mmol), AgSCF3 (2.0 mmol) TsOH·H2O (2.0 mmol), and MeCN (4.0 mL). The tube was then placed in an autoclave that was sealed, purged three times with N2, and heated in an oil bath at 40 °C for 8 h. The autoclave was then cooled to r.t. and the crude product was purified by column chromatography (silica gel, PE–EtOAc). N-(4-Methoxyphenyl)-3-[(trifluoromethyl)sulfanyl]propenamide (3a) Prepared according to the general procedure, and purified by column chromatography [silica gel, PE–EtOAc (10:1 to 6:1)] to give a white solid; yield: 145.1 mg (52%). 1H NMR (400 MHz, CDCl3): δ = 7.78 (s, 1 H), 7.34 (d, J = 8.8 Hz, 2 H), 6.81 (d, J = 8.8 Hz, 2 H), 3.76 (s, 3 H), 3.18 (t, J = 6.8 Hz, 2 H), 2.70 (t, J = 6.8 Hz, 2 H). 13C NMR (101 MHz, CDCl3): δ = 168.6, 156.7, 131.1 (q, J = 304.4 Hz), 130.4, 122.5, 114.1, 55.4, 36.9, 25.3. 19F NMR (376 MHz, CDCl3): δ = –41.23 (s, 3 F). HRMS (ESI): m/z [M + Na]+ calcd for C11H12F3NNaO2S: 302.0435; found: 302.0433.