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Synlett 2024; 35(20): 2508-2514
DOI: 10.1055/a-2384-6655
DOI: 10.1055/a-2384-6655
letter
Special Issue to Celebrate the 75th Birthday of Prof. B. C. Ranu
Fe(II)-Catalyzed Metal–Ligand Cooperative Approach for Selective C3-Alkylation of Indoles
The research was supported by the Ministry of Education, India(STARS, Project STARS2/2023-0450) and the CSIR (Project: 01(3023)/21/EMR-II). The Department of Science and Technology, India funded SAIF facility at IIESTS is acknowledged for providing NMR and HRMS facilities.
Abstract
Herein, we report a straightforward approach for synthesizing C3-alkylated indoles selectively via an iron-catalyzed alkylation of indoles using alcohols as the alkylating agents. A well-defined, air-stable, and easy-to-prepare Fe(II) catalyst of a redox-active tridentate arylazo scaffold was used as a catalyst. Various C3-alkylated indoles were prepared selectively in moderate to good isolated yields by coupling indoles with different substituted alcohols. The methodology is compatible with the gram-scale synthesis. Control experiments were performed to unveil the mechanism, which revealed that the alkylation reaction proceeds via borrowing-hydrogen pathway where the coordinated azo-aromatic ligand actively participates during catalysis, acting as an electron and hydrogen reservoir.
Key words
iron catalysis - metal–ligand cooperativity - borrowing hydrogen approach - C3-alkylated indole - alcoholsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2384-6655.
- Supporting Information
Publication History
Received: 30 June 2024
Accepted after revision: 12 August 2024
Accepted Manuscript online:
12 August 2024
Article published online:
27 September 2024
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- 19 General Procedure for C3-Alkylation of Indoles (4a–t) In a 15 mL oven-dried high-pressure tube, respective indoles (1 equiv., 1.0 mmol), alcohols (2.5 equiv., 2.5 mmol), KOH (0.7 mmol, 39.2 mg), Zn dust (0.7 mmol, 47 mg), 1a (3.0 mol%, 13.4 mg), and a tiny magnetic stir bar were added under an argon atmosphere, and the tube was tightly capped with a PTFE screw cap and then placed in an oil bath preheated to 140 °C. The reaction was continued for 16 h. After completion of the reaction, the mixture was diluted with ethyl acetate and passed through a Celite pad. The solvent and the volatiles were evaporated under a vacuum, and the crude reaction mixture was purified by column chromatography using hexane and ethyl acetate as the eluent.
For C3-alkylated indoles:
Classical approach:
For Pt-catalyzed C3-alkylation of indoles:
For Pd-catalyzed C3-alkylation of indoles:
For Ru-catalyzed C3-alkylation of indoles:
For Ir-catalyzed C3-alkylation of indoles:
For Mn-catalyzed C3-alkylation of indoles:
For Co-catalyzed C3-alkylation of indoles:
For Ni-catalyzed C3-alkylation of indoles:
Use of iron in catalysis: