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Synlett 2020; 31(02): 194-198
DOI: 10.1055/s-0039-1691532
DOI: 10.1055/s-0039-1691532
letter
Transition-Metal-Free Aerobic Oxidative Cross-Coupling of Indoles with Arylidenemalononitriles
The authors thank the National Natural Science Foundation of China (21462038) for the financial support of this work.
Weitere Informationen
Publikationsverlauf
Received: 09. Oktober 2019
Accepted after revision: 01. Dezember 2019
Publikationsdatum:
10. Dezember 2019 (online)
Abstract
An efficient method for the direct construction of C(sp2)–C(sp2) bonds by aerobic oxidative cross-coupling of indoles with arylidenemalononitriles is described. Various [aryl(1H-indol-3-yl)methylene]malononitriles were efficiently synthesized by using air as an oxidant under mild conditions. The salient features for this protocol are no transition-metal catalysts, no organometallic reagents, high atom economy, high yield, mild conditions, and simple workup procedures.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1691532.
- Supporting Information
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- 6 [Aryl(1H-indol-3-yl)methylene]malononitriles 2a–v; General Procedure A mixture of the appropriate arylidenemalononitrile 1 (0.5 mmol), indole (0.5 mmol), and KOH (1.0 mmol) in 1,4-dioxane (4 mL) was stirred at 60 °C for 2 h. When the reaction was complete (TLC), the mixture was extracted with EtOAc (3 × 10 mL), and the extracts were washed with sat. brine (3 × 10 mL). The organic phase was dried (Na2SO4) and concentrated under reduced pressure, and the residue was purified by column chromatography [silica gel, PE–EtOAc (2:1)]. [1H-Indol-3-yl(phenyl)methylene]malononitrile (2a) Yellow solid; yield: 110 mg (82%); mp 166–170 °C. 1H NMR (600 MHz, DMSO-d 6): δ = 12.60 (s, 1 H), 8.34 (s, 1 H), 7.65 (t, J = 7.2 Hz, 1 H), 7.57–7.51 (m, 5 H), 7.19–7.15 (m, 1 H), 6.96–6.93 (m, 1 H), 6.38 (d, J = 8.1 Hz, 1 H). 13C NMR (150 MHz, DMSO-d 6): δ = 168.46, 137.58, 136.78, 134.99, 132.38, 130.30, 129.31, 126.13, 123.64, 122.15, 120.80, 116.75, 116.03, 113.52, 112.65, 72.09. HRMS (ESI): m/z [M + H]+ calcd for C18H12N3: 270.1026; found: 270.1023. [(5-Methoxy-1H-indol-3-yl)(phenyl)methylene]malononitrile (2p) Yellow solid; yield: 117 mg (78%); mp 231–233 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 12.56 (s, 1 H), 8.28 (s, 1 H), 7.69–7.64 (m, 1 H), 7.58 (t, J = 7.6 Hz, 2 H), 7.52 (dd, J = 8.4, 1.4 Hz, 2 H), 7.43 (d, J = 8.8 Hz, 1 H), 6.82 (dd, J = 8.9, 2.4 Hz, 1 H), 5.79 (d, J = 2.4 Hz, 1 H), 3.43 (s, 3 H). 13C NMR (150 MHz, DMSO-d 6): δ = 168.32, 155.38, 136.90, 135.12, 132.35, 132.10, 130.17, 129.36, 126.98, 116.88, 116.18, 114.24, 113.28, 112.58, 103.37, 71.00, 55.27. HRMS (ESI): m/z [M + H]+ calcd for C19H14N3O: 300.1131; found: 300.1132.