Ruthenium-Catalyzed Oxidative Dearomatization of Indoles for the Construction of C2-Quaternary Indolin-3-ones

Abstract

A ruthenium-catalyzed oxidative dearomatization of 2-alkyl- or 2-aryl-substituted indoles has been developed. When coupled with a cascade transformation, it provides a new system for the construction of indolin-3-ones bearing a C2-quaternary functionality. The reaction occurs readily with RuCl₃·3H₂O as a catalyst in acetonitrile. 2-(3-Indolyl)-substituted indolin-3-ones were obtained in medium to high yields. A mechanism for the reaction is also proposed.

Key words

ruthenium catalysis - oxidation - dearomatization - indoles - indolinones

• References and Notes

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• 21 Ruthenium-Catalyzed Oxidative Dearomatization of Indoles 1; General Procedure A mixture of indole 1 (0.50 mmol), NaIO₄ (107 mg, 0.50 mmol, 1.0 equiv), and RuCl₃·3H₂O (6.5 mg, 0.025 mmol, 5.0 mol%) in MeCN (3 mL) was added to a 25 mL Schlenk flask at r.t. and the mixture was then stirred at 70 °C until the reaction was complete. Then the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography [silica gel, PE–EtOAc (10:1 to 5:1)]. 2,2′-Diphenyl-1,2-dihydro-1′H,3H-2,3′-biindol-3-one (2a) Yellow solid; yield: 97.0 mg (97%); mp 220–223 °C. IR (neat): 3058, 3025, 2910, 1696, 1618, 1470, 1439, 1074, 1026, 919, 742 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 11.34 (s, 1 H), 8.33 (s, 1 H), 7.51 (dd, J = 8.3, 7.1 Hz, 1 H), 7.39–7.33 (m, 3 H), 7.25 (d, J = 7.7 Hz, 1 H), 7.16–7.11 (m, 3 H), 7.06–7.01 (m, 6 H), 6.98 (d, J = 8.3 Hz, 1 H), 6.78–6.69 (m, 2 H), 6.61 (d, J = 8.0 Hz, 1 H). ¹³C NMR (126 MHz, DMSO-d ₆): δ = 200.5, 160.1, 139.8, 138.0, 137.5, 135.8, 133.2, 129.5, 127.6, 127.4, 127.0, 124.4, 121.2, 120.3, 118.7, 118.5, 117.5, 111.9, 111.3, 111.0, 71.2. HRMS (ESI): m/z [M + Na]⁺ Calcd for C₂₈H₂₀N₂NaO: 423.1473; found: 423.1477.