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Synlett 2014; 25(16): 2301-2305
DOI: 10.1055/s-0034-1378613
DOI: 10.1055/s-0034-1378613
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One-Step Synthesis of Quinolines via Palladium-Catalyzed Cross-Coupling of Cyclopropanols with Unprotected ortho-Bromoanilines
Further Information
Publication History
Received: 15 May 2014
Accepted after revision: 23 July 2014
Publication Date:
21 August 2014 (online)
Abstract
The cross-coupling of unprotected ortho-bromoanilines with cyclopropanols yields quinolines in a single operation via an intramolecular condensation and palladium-catalyzed oxidation sequence. The reaction tolerates a variety of cyclopropanols and substituted bromoanilines. Deuterium-labeling experiments provide direct evidence of a second equivalent of bromoaniline serving as the terminal oxidant.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083. Included are 1H, 13C, 2H, and 19F NMR spectra for all quinolines reported herein.
- Supporting Information
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References and Notes
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- 10 Synthesis of Quinoline 1A – Representative Procedure An oven-dried vial equipped with stir bar was charged with Pd(OAc)2 (0.0055 g, 0.0245 mmol, 0.10 equiv), dppb (0.020 g, 0.0489 mmol, 0.2 equiv), and K2CO3 (0.15 g, 0.98 mmol, 4.0 equiv). Freshly distilled toluene was introduced into the vial via syringe, and the contents were allowed to stir. A second oven-dried vial equipped with a stir bar was charged with cyclopropanol A (0.05 g, 0.245 mmol, 1.0 equiv) and 2-bromoaniline (0.084 g, 0.489 mmol, 2.0 equiv). Freshly distilled toluene was introduced into the vial via syringe, and contents were allowed to stir. The solution of substrates was added to the solution containing the palladium catalyst. The reaction vial was purged with argon, capped with a rubber septum, and heated to 110 °C for 24 h. Upon completion, the reaction mixture was filtered through a pad of Celite using EtOAc and concentrated in vacuo. The crude product was purified by flash column chromatography, eluting with the indicated solvent mixture to afford the desired quinoline product. Purification by flash column chromatography using 20% EtOAc in hexanes provided the desired quinoline as a pale yellow oil (0.051 g, 0.19 mmol) in 76% yield. 1H NMR (400 MHz, CDCl3): δ = 8.13 (d, J = 8.4 Hz, 1 H), 8.04 (d, J = 8.4 Hz, 1 H), 7.78 (d, J = 8.1 Hz, 1 H), 7.73 (dd, J = 8.4, 7.8 Hz, 1 H), 7.52 (dd, J = 8.4, 7.8 Hz,1 H), 7.36 (d, J = 8.1 Hz, 1 H), 7.30–7.26 (m, 3 H), 4.36 (s, 2 H), 1.33 (s, 9 H). 13C NMR (100 MHz, CDCl3): δ = 161.4, 149.2, 147.8, 136.3, 136.1, 129.3, 128.9, 128.8, 127.4, 126.7, 125.8, 125.4, 121.5, 45.0, 34.3, 31.3. IR: ν = 3057, 2960, 1655, 1618, 1599, 1504, 742 cm–1. HRMS: m/z calcd for [C20H21N]+: 275.1674; found: 275.1669.