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Synlett 2014; 25(16): 2350-2354
DOI: 10.1055/s-0034-1378615
DOI: 10.1055/s-0034-1378615
letter
Synthesis of Tetracyclic Flavonoids via Palladium-Catalyzed Intramolecular Oxidative Cyclization
Further Information
Publication History
Received: 16 May 2014
Accepted after revision: 16 July 2014
Publication Date:
18 August 2014 (online)
Dedicated to Professors Charles J. Kelley and Scott D. Rychnovsky
Abstract
Palladium-catalyzed oxidative cyclization of terminal-olefin-tethered phenols was achieved in good yields (61–90% yields). The reaction was optimized and White catalyst {[1,2-bis-(phenylsulfinyl)ethane]palladium(II)acetate} provided the best yield in the presence of benzoquinone as an oxidant. The reaction tolerated both electron-donating and electron-withdrawing substituents on the substrates, and the structure of the tetracyclic flavonoids was confirmed using single-crystal X-ray analysis. The study represents the first example of successful allylic C–H activation/ C–O bond formation using terminal-olefin-tethered phenols.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
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- 13 General Procedure for Compound 7f A dry two-neck round-bottom flask was charged with White catalyst (0.027 g, 0.053 mmol, 0.2 equiv) and benzoquinone (0.059 g, 0.55 mmol, 2 equiv). Compound 6f (0.09 g, 0.27 mmol, 1 equiv) and AcOH (0.018 g, 0.29 mmol, 1.1 equiv) in CH2Cl2 (5 mL) was added dropwise to the above mixture and refluxed for 5 h. To the reaction mixture, sat. NH4Cl was added, and the mixture was extracted with CH2Cl2. The organic phase was washed with brine, dried over Na2SO4, and evaporated. The crude product was purified by silica gel column chromatography by eluting with EtOAc–hexanes (5%) to afford 7f (79 mg, 87%). Spectral Data White solid; yield 79 mg (87%); mp 171–172 °C. IR (KBr): 3020 (w), 1635 (s), 1612 (s), 1216 (s), 832 (m), 772 (s) cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.51 (s, 3 H), 5.16 (dt, J = 10.4, 1.3 Hz, 1 H), 5.34 (dt, J = 17.1, 1.2 Hz, 1 H), 5.99 (ddd, J = 17.1, 10.5, 5.0 Hz, 1 H), 6.15 (dt, J = 5.0, 1.5 Hz, 1 H), 7.01 (dd, J = 8.3, 0.7 Hz, 1 H), 7.07 (td, J = 7.6, 1.0 Hz, 1 H), 7.41 (ddd, J = 8.3, 7.4, 1.7 Hz, 1 H), 7.44 (s, 1 H), 7.78 (dd, J = 7.8, 1.5 Hz, 1 H), 8.16 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ = 20.8, 72.9, 111.9, 115.6, 117.0, 117.7, 119.9, 121.7, 123.2, 123.7, 125.5, 131.9, 134.0 (2×), 142.9, 153.9, 154.9, 156.1, 173.5. ESI-MS: m/z = 325.1 [M + H]+.
- 14 CCDC 1017874.