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Synlett 2017; 28(19): 2670-2674
DOI: 10.1055/s-0036-1589079
DOI: 10.1055/s-0036-1589079
letter
Iron-Catalyzed C3-Formylation of Indoles with Formaldehyde and Aqueous Ammonia under Air
We thank the National High Technology Research and Development Program of China (2007AA02Z301), the Natural Science Foundation of Jiangsu Province (BK20141257), the Natural Science Foundation of Yancheng Teachers University (09YCKL021, 14YCKL001), and the Fundamental Research Funds for the Central University (WY111307) for their generous financial supportFurther Information
Publication History
Received: 22 May 2017
Accepted after revision: 23 June 2017
Publication Date:
14 August 2017 (online)
Abstract
An efficient iron-catalyzed C3-selective formylation of free (N–H) or N-substituted indoles was developed by employing formaldehyde and aqueous ammonia, with air as the oxidant. This new method gave 3-formylindoles in moderate to excellent yields with fairly short reaction times. Moreover, this procedure for catalytic formylation of indoles can be applied to gram-scale syntheses.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1589079.
- Supporting Information
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- 13 Indolecarbaldehydes 2a–2aa; General Procedure A 50 mL round-bottomed flask equipped with a magnetic stirring bar was charged with the appropriate indole 1 (0.5 mmol, 1.0 equiv), 37% aq HCHO (0.5 mmol, 0.0406 g, 1.0 equiv), 25% aq NH3 (1.0 mmol, 0.0681 g, 2.0 equiv), FeCl3 (0.01 mmol, 0.0016 g, 2 mol%), and DMF (2 mL). The flask was fitted with a reflux condenser, and the mixture was stirred at 130 °C under open air. When the reaction was complete (TLC), the mixture was cooled to r.t., diluted with sat. aq NaCl (10 mL) and 0.5 M aq HCl (2 mL), and extracted with EtOAc (3 x 7 mL). The organic layers were combined, washed with sat. aq NaHCO3 (10 mL) and sat. aq NaCl (10 mL), dried (Na2SO4), and concentrated under reduced pressure. The residue was purified by flash column chromatography (silica gel, hexane–EtOAc). 1H-indole-3-carbaldehyde (2a)7f Pale-yellow solid; yield: 0.0676 g (93%); mp 190–192 °C. 1H NMR (400 MHz, CDCl3): δ = 10.07 (s, 1 H), 8.36 – 8.28 (m, 1 H), 7.86 (d, J = 3.0 Hz, 1 H), 7.48 – 7.41 (m, 1 H), 7.36 – 7.31 (m, 2 H). 13C NMR (126 MHz, DMSO-d 6): δ = 185.01, 138.30, 137.05, 124.08, 123.49, 122.15, 120.83, 118.13, 112.38. EI-MS: m/z (%) = 63(30), 90(60), 116(18), 144(100), 145(84) [M+]
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