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CC BY 4.0 · Synlett 2025; 36(07): 849-852
DOI: 10.1055/a-2415-3708
DOI: 10.1055/a-2415-3708
letter
Ruthenium(II)-Catalyzed C–H Allylation of N,N-Dialkylthiobenzamides with Allyl Methyl Carbonate by Sulfur Coordination
This work was supported by the National Natural Science Foundation of China (22171034), the Natural Science Foundation of Liaoning Province (2023MS116), and the Fundamental Research Funds for the Central Universities (DUT22LAB606).
Abstract
This report describes a Ru(II)-catalyzed C–H allylation of N,N-dialkylthiobenzamides with allyl methyl carbonate. The reaction is carried out using [RuCl2(p-cymene)]2 in the presence of Cu(OAc)2 and Ag2O. This method represents the first example of a Ru-catalyzed C–H allylation directed by a sulfur-containing group. As a further advantage, the method is performed in sustainable and ecofriendly MeCN as the solvent.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2415-3708.
- Supporting Information
Publication History
Received: 06 March 2024
Accepted after revision: 06 May 2024
Accepted Manuscript online:
13 September 2024
Article published online:
15 October 2024
© 2024. This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)
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- 15 Allylation of N,N-Dialkylthiobenzamides; General Procedure A pressure tube was charged with [RuCl2(p-cymene)]2 (10 mol%), Cu(OAc)2 (2.0 equiv), Ag2O (0.5 equiv), K2CO3 (2.0 equiv), the appropriate N,N-dialkylthiobenzamide 1 (0.20 mmol, 1.0 equiv), and allyl methyl carbonate (2; 2.0 equiv). MeCN (1.5 mL) was then added with vigorous stirring at r.t. The tube was placed in an oil bath, and the mixture was stirred for the appropriate time at 100 °C. The mixture was then diluted with EtOAc (20 mL), filtered, and concentrated. The crude product was purified by column chromatography [silica gel, hexanes–EtOAc (10:1)]. 1-[(2-Allylphenyl)carbonothioyl]pyrrolidine (3a) Yellow oil; yield: 77%. 1H NMR (500 MHz, CDCl3): δ = 7.23 (d, J = 11.4 Hz, 3 H), 7.09 (d, J = 7.1 Hz, 1 H), 5.92 (ddd, J = 24.1, 9.0, 7.0 Hz, 1 H), 5.07 (dd, J = 24.7, 13.5 Hz, 2 H), 4.03 (dt, J = 13.8, 6.8 Hz, 1 H), 3.91 (dt, J = 14.2, 7.3 Hz, 1 H), 3.51 (dd, J = 15.2, 8.1 Hz, 1 H), 3.38 (dd, J = 15.2, 5.4 Hz, 1 H), 3.34–3.24 (m, 1 H), 3.26–3.11 (m, 1 H), 2.10–2.01 (m, 2 H), 1.93 (dp, J = 19.8, 6.5 Hz, 2 H). 13C NMR (126 MHz, CDCl3): δ = 196.58, 136.53, 133.84, 129.96, 128.81, 126.65, 124.86, 116.19, 53.03, 52.41, 37.18, 26.19, 24.60. HRMS (ESI): m/z [M + H]+ calcd for C14H18NS: 232.35; found: 232.19.