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Synlett 2023; 34(15): 1791-1794
DOI: 10.1055/s-0041-1738438
DOI: 10.1055/s-0041-1738438
letter
A New Approach to the S–H Insertion Reaction of α-Keto Esters and Thiols
This work was financially supported by the Fundamental Research Program of Shanxi Province (Grant No. 20210302123016) and the Applied Basic Research Project of Shanxi Province (Grant No. 201901D211220).
Abstract
Sulfur-containing compounds are well known for their frequent occurrence in a large number of natural and synthetic molecules with relevant biological activity. An easy and highly efficient approach to sulfur-containing compounds, by S–H insertion reactions of α-keto esters with thiols, is reported. The substrate scope was remarkably wide, affording the corresponding products in up to 97% yield. Overall, the raw materials were readily available and the reaction conditions were mild in this synthetic method.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0041-1738438.
- Supporting Information
Publication History
Received: 06 March 2023
Accepted after revision: 12 April 2023
Article published online:
12 May 2023
© 2023. Thieme. All rights reserved
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- 16 General procedure: P(NMe2)3 (0.15 mmol) was added to a solution of α-keto ester (2, 0.1 mmol) in dry DCM (0.5 mL) at –78 °C, and the resulting mixture was stirred for 5 min at the same temperature. Thiol (1, 0.1 mmol) was then added to the above solution at –78 °C. After being stirred for 5 min at –78 °C, the mixture was left to stir at room temperature for 8 h. After the reaction had finished, the solution was concentrated under reduced pressure, and the mixture was purified by flash column chromatography over silica gel (petroleum ether/ethyl acetate = 15:1 or 10:1) to afford the desired product 3, which was analyzed with 1H NMR and 13C NMR spectroscopy (see Supporting Information). Typical data for representative compound 3aa: Rf = 0.30 (petroleum ether/ethyl acetate = 10:1), colorless oil (26.4 mg, 97% yield). 1H NMR (600 MHz, CDCl3) δ = 7.45 (d, J = 7.2 Hz, 2 H), 7.39–7.37 (m, 2 H), 7.35–7.29 (m, 3 H), 7.28–7.24 (m, 3 H), 4.90 (s, 1 H), 4.18–4.07 (m, 2 H), 1.16 (t, J = 7.2 Hz, 3 H). 13C NMR (150 MHz, CDCl3): δ = 170.6, 135.7, 133.9, 132.7, 129.1, 128.8, 128.6, 128.4, 128.1, 61.9, 56.4, 14.1. HRMS (ESI): m/z calcd for C16H16O2SNa [M + Na]+: 295.0763; found: 295.0769.