Rhodium-Catalyzed Decarbonylative Intramolecular Arylation of 2-(1H-Indole-1-carbonyl)benzoic Acids

Abstract

We developed a redox-neutral synthesis of isoindoloindolone via intramolecular arylation of 2-(1H-indole-1-carbonyl)benzoic acids. This protocol facilitates the formation of various substituted isoindoloindolones in yields ranging from 17% to 80%. Our mechanistic investigations indicate the pivotal role of NaI: the iodide anion promotes the formation of the desired isoindoloindolone, and the sodium cation suppresses the formation of acylated byproducts, thereby enabling the selective formation of isoindoloindolones in acceptable yields.

Key words

rhodium - intramolecular arylation - mixed anhydride - isoindoloindolones - C–H activation - indoles

Publication History

Received: 15 February 2024

Accepted after revision: 28 February 2024

Accepted Manuscript online:
28 February 2024

Article published online:
20 March 2024

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• 14 Typical Experimental Procedure for the Rhodium-Catalyzed Decarbonylative Intramolecular Arylation of Benzoic Acids 1 To an oven-dried test tube equipped with a stirring bar were added benzoic acid 1 (0.3 mmol), [RhCl(nbd)]₂ (6.9 mg, 0.015 mmol), and NaI (11.2 mg, 0.075 mmol), followed by the addition of 1,4-dioxane (0.6 mL). Subsequently, Piv₂O (83.8 mg, 91 μL, 0.45 mmol) was injected into the solution via a syringe, and the tube was sealed with a PTFE-lined cap. The reaction mixture was stirred at 170 °C for 18 h. After cooling to room temperature, the mixture was filtered through a pad of silica gel (EtOAc/hexane = 1:1). The filtrate was concentrated under reduced pressure, and the residue was purified by preparative thin-layer chromatography to yield product 2. 1-Methyl-6H-isoindolo[2,1-a]indol-6-one (2c) The title compound was obtained as a yellow solid (54.6 mg, 78%); purified by preparative TLC (dichloromethane/toluene/hexane = 1:1:2); mp 143.2–143.8 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.68–7.62 (m, 2 H), 7.45–7.37 (m, 2 H), 7.27–7.21 (m, 1 H), 7.11 (t, J = 7.7 Hz, 1 H), 6.88 (d, J = 7.4 Hz, 1 H), 6.53 (s, 1 H), 2.40 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 162.5, 138.0, 134.6, 133.9, 133.6, 133.5, 133.2, 131.8, 128.5, 126.2, 125.0, 124.4, 120.9, 110.7, 101.9, 18.3. IR (neat): 3424, 3115, 2100, 1733, 1621, 1494, 1468, 1448, 1386, 1282, 1218, 1183, 1145, 1080, 906, 827, 778, 759, 693, 545 cm^–1. HRMS (ESI-TOF): m/z calcd for C₁₆H₁₁NNaO⁺ [M + Na]⁺: 256.0733; found: 256.0736. 2-Bromo-6H-isoindolo[2,1-a]indol-6-one (2i) The title compound was obtained as a yellow solid (41.8 mg, 47%); purified by preparative TLC (dichloromethane/toluene/hexane = 1:1:1); mp 174.1–175.0 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.77–7.69 (m, 2 H), 7.58–7.46 (m, 3 H), 7.39–7.31 (m, 2 H), 6.50 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 162.3, 139.8, 136.1, 134.2, 133.9, 133.6, 132.1, 129.2, 128.9, 125.4, 124.9, 121.4, 116.9, 114.4, 102.3. IR (neat): 3116, 1728, 1621, 1437, 1380, 1355, 1318, 1174, 1140, 1047, 865, 798, 759, 695 cm^–1. HRMS (ESI-TOF): m/z calcd for C₁₅H₈ ⁷⁹BrNNaO⁺ [M + Na]⁺: 319.9681; found: 319.9669.