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Synlett 2020; 31(14): 1394-1399
DOI: 10.1055/s-0040-1707099
DOI: 10.1055/s-0040-1707099
letter
Visible-Light-Enabled Aerobic Denitrative C3-Alkenylation of Indoles with β-Nitrostyrenes
R.C. is grateful to Department of Science and Technology, Ministry of Science and Technology, India for the award of DST WOS-A project (Grant No. SR/WOS-A/CS-54/2018) and financial support.Further Information
Publication History
Received: 15 March 2020
Accepted after revision: 06 April 2020
Publication Date:
22 April 2020 (online)
Abstract
Herein, we unveil the first visible-light-mediated alkenylation reaction of indoles. The reaction follows a denitrative radical pathway where β-nitrostyrenes have been utilized as the alkene precursors for the C3-styrenylation of indoles under visible-light irradiation to afford biologically and synthetically important 3-alkenylindoles. High regioselectivity, absence of any photocatalyst, metal, external oxidant, acid or base, and the use of visible light and air as inexpensive clean reagents are the key highlights of the developed method.
Key words
indoles - β-nitrostyrenes - 3-alkenylindoles - visible light - radical reaction - photocatalyst-freeSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707099.
- Supporting Information
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- 17 General Procedure for the Synthesis of 3-Alkenylindoles 3 A mixture of indole 1 (1.5 mmol) and β-nitrostyrene (2, 1.0 mmol) in CH3CN (3 mL) was irradiated with visible light (white-light-emitting diode, 7.0 W) at a distance of 0.75 cm in a 10 mL round-bottom flask with stirring at r.t. for 18 h. Upon completion of the reaction (monitored by TLC), water (5 mL) was added, and the mixture was extracted with EtOAc (3 × 15 mL). The combined organic phases were dried with anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (EtOAc/n-hexane, 1:19) to afford an analytically pure sample of 3-alkenylindole 3. Characterization Data of Representative 3-Alkenylindoles 3 (E)-3-(4-Methoxystyryl)-1H-indole (3c) 18,9b 1H NMR (400 MHz, DMSO): δ = 11.25 (s, 1 H), 7.98 (d, J = 8.0 Hz, 1 H), 7.58 (d, J = 2.4 Hz, 1 H), 7.50 (d, J = 8.8 Hz, 2 H), 7.42 (d, J = 8.0 Hz, 1 H), 7.26 (d, J = 16.6 Hz, 1 H), 7.15 (t, J = 7.6 Hz, 1 H), 7.10 (t, J = 6.9 Hz, 1 H), 7.04 (d, J = 16.4 Hz, 1 H), 6.92 (d, J = 8.2 Hz, 2 H), 3.76 (s, 3 H). 13C NMR (100 MHz, DMSO): δ = 158.0, 137.0, 131.2, 126.6, 125.3, 125.2, 123.2, 121.7, 120.3, 119.8, 119.5, 114.1, 113.9, 111.9, 55.1. HRMS (ESI): m/z calcd for C17H16NO [M + H]+: 250.1226; found: 250.1196. 3-[(E)-2-(Thiophen-2-yl)vinyl]-1H-indole (3i) 18,19 1H NMR (400 MHz, DMSO): δ = 11.34 (s, 1 H), 7.94 (d, J = 7.6 Hz, 1 H), 7.64 (s, 1 H), 7.41 (d, J = 7.6 Hz, 1 H), 7.32–7.31 (m, 2 H), 7.17–7.10 (m, 4 H), 7.01 (s, 1 H). 13C NMR (100 MHz, DMSO): δ = 144.1, 137.0, 127.8, 126.4, 124.9, 124.3, 123.0, 122.3, 121.8, 119.8, 119.7, 117.1, 113.2, 111.9. HRMS (ESI): m/z calcd for C14H12NS [M + H]+: 226.0685; found: 226.0681. (E)-5-Fluoro-3-styryl-1H-indole (3l) 19 1H NMR (400 MHz, DMSO): δ = 11.47 (s, 1 H), 7.82 (d, J = 10.0 Hz, 1 H), 7.75 (s, 1 H), 7.60 (d, J = 7.2 Hz, 2 H), 7.45–7.41 (m, 2 H), 7.35 (t, J = 6.8 Hz, 2 H), 7.19 (t, J = 6.6 Hz, 1 H), 7.10 (d, J = 17.1 Hz, 1 H), 7.03 (t, J = 8.4 Hz, 1 H). 13C NMR (100 MHz, DMSO): δ = 159.0, 138.9, 134.0, 129.0, 128.1, 126.7, 126.0, 125.8, 123.9, 122.4, 114.4, 113.3, 110.4, 105.3. HRMS (ESI): m/z calcd for C16H13FN [M + H]+: 238.1027; found: 238.1007.
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