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Synlett 2015; 26(05): 651-655
DOI: 10.1055/s-0034-1379885
DOI: 10.1055/s-0034-1379885
letter
Metal-Free N-Arylation of Indolines with Diaryliodonium Salts
Weitere Informationen
Publikationsverlauf
Received: 05. November 2014
Accepted after revision: 27. November 2014
Publikationsdatum:
14. Januar 2015 (online)
Abstract
The N-arylation of indolines using diaryliodonium salts as electrophilic arylating reagents is described. Without the use of any additional additives, the desired N-aryl indolines could be obtained in up to 85% yield.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1379885.
- Supporting Information
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References and Notes
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- 27 General Procedure for the N-Arylation of Indoline (1a) with Diphenyliodonium Triflate (2a) to 1-Phenylindoline (3a) Diphenyliodonium triflate (2a, 0.1 g, 0.23 mmol, 1.1 equiv) was charged in a vial and sealed with a septum. After adding TFE (3 mL), indoline (1a, 0.024 mL, 0.21 mmol) was added dropwise slowly to the solution, which was then heated to 70 °C for 14 h. After the solution was cooled to r.t., the mixture was diluted with H2O and sat. NaHCO3. The aqueous phase was extracted several times with CH2Cl2. The organic phase is washed with H2O, dried over MgSO4, filtered, and concentrated in vacuo. The crude residue was purified by column chromatography on silica gel, eluting with cyclohexane–CH2Cl2 (2:1, v/v) giving 34 mg (83%) of 3a as a colorless solid. 2,3-Dihydro-1-(4-methylphenyl)-1H-indole (3b) Pale yellow oil, partially crystalline (18 mg, 41%); eluent: cyclohexane–CH2Cl2 (20:1 → 15:1 → 10:1, v/v); mp 66–70 °C. 1H NMR (400 MHz, CDCl3): δ = 7.17–7.13 (m, 5 H), 7.07–7.04 (m, 2 H), 6.75–6.69 (m, 1 H), 3.93 (t, 2 H, J = 8.5 Hz), 3.12 (t, 2 H, J = 8.5 Hz), 2.33 (s, 3 H). 13C{1H} NMR (100.6 MHz, CDCl3): δ = 147.7, 141.9, 131.2, 130.8, 129.8, 127.2, 125.1, 118.6, 118.3, 108.0, 52.5, 28.3, 20.9. IR (neat): 2360, 2341, 1770, 1742, 1597, 1515, 1482, 1456, 1384, 1312, 1296, 1246, 1166, 1127, 1063, 1049, 924, 869, 815, 742, 703 cm–1. HRMS (APCI): m/z calcd for C15H15N: 209.12045; found [M + H]+: 210.12714. 1-(4-Chlorophenyl)-2-methylindoline (6f) Pale yellow oil (15 mg, 29%); eluent: cyclohexane–CH2Cl2 (5:1, v/v). 1H NMR (500 MHz, CDCl3): δ = 7.31 (d, 2 H, J = 8.8 Hz), 7.18 (d, 2 H, J = 8.8 Hz), 7.14 (d, 1 H, J = 7.2 Hz), 7.03 (t, 1 H, J = 7.5 Hz), 6.78 (d, 1 H, J = 7.9 Hz), 6.74 (t, 1 H, J = 7.4 Hz), 4.36–4.30 (m, 1 H), 3.33 (dd, 1 H, J 1 = 8.8 Hz, J 2 = 15.5 Hz), 2.76 (dd, 1 H, J 1 = 7.4 Hz, J 2 = 15.4 Hz), 1.31 (d, 3 H, J = 6.1 Hz). 13C{1H} NMR (125.8 MHz, CDCl3): δ = 148.4, 142.3, 129.7, 129.4, 127.7, 127.3, 125.1, 122.9, 119.3, 108.5, 60.1, 37.3, 20.1. HRMS (APCI): m/z calcd for C15H14ClN: 243.08148 (100%), found [M + H]+: 244.08851.