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Synlett 2020; 31(14): 1400-1403
DOI: 10.1055/s-0040-1707162
DOI: 10.1055/s-0040-1707162
letter
Iron-Catalyzed Direct Cross-Coupling of Ethers and Thioether with Alcohols for the Synthesis of Mixed Acetals
This work was sponsored by the Natural Science Foundation of China (21776139, 21302099), the Natural Science Foundation of Jiangsu Province (BK20161553), the Natural Science Foundation of Jiangsu Provincial Colleges and Universities (16KJB150019), the China Scholarship Council, the Qing Lan project of Nanjing Normal University, and the Priority Academic Program Development of Jiangsu Higher Education Institutions.
Further Information
Publication History
Received: 13 April 2020
Accepted after revision: 28 May 2020
Publication Date:
23 June 2020 (online)
§ These authors contributed equally to this work.
Abstract
An iron-catalyzed direct O-alkylation of alcohols via α-C(sp3)–H activation of ethers and a thioether has been established that tolerates cyclic and acyclic ethers and alcohols containing aromatic N-heterocyclic moieties, providing an efficient and green method for the synthesis of mixed acetals with good to excellent yields. The robustness of this protocol is demonstrated by the late-stage oxidation of a structurally complex natural product.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707162.
- Supporting Information
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- 22 Typical procedure for the synthesis of 3ba: A 25 mL flask equipped with a magnetic stir bar was charged with FeBr2 (5.5 mg, 0.025 mmol), 2-(4-methoxyphenyl)ethanol 1b (39.2 mg, 0.25 mmol), PMHS (170 μL, 0.75 mmol), DTBP (94 μL, 0.5 mmol) and THF (2 mL) before standard cycles evacuation and backfilling with dry N2. The mixture was then stirred at 80 °C for 3 h. After cooling to room temperature, the reaction mixture was diluted with water (15 mL) and extracted with diethyl ether (3 × 15 mL). The organic phases were combined, and the volatile components were evaporated in a rotary evaporator. The residue was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 50:1) to afford 3ba (49.0 mg, 90%) as a colorless liquid. 1H NMR (400 MHz, CDCl3): δ = 7.18 (dt, J 1 = 8.73 Hz, J 2 = 2.54 Hz, 2 H), 6.87 (dt, J 1 = 8.73 Hz, J 2 = 2.54 Hz, 2 H), 5.15 (q, J = 2.07 Hz, 1 H), 3.90–3.82 (m, 3 H), 3.80 (s, 3 H), 3.62 (dt, J 1 = 9.72 Hz, J 2 = 4.84 Hz, 1 H), 2.86 (t, J = 7.23 Hz, 2 H), 2.03–1.79 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ = 157.9, 131.0, 129.7, 113.6, 103.7, 68.1, 66.7, 55.1, 35.3, 32.2, 23.4.