K2S2O8-Mediated Arylmethylation of Indoles with Tertiary Amines via sp3 C–H Oxidation in Water

Manjula Singh; Arvind K. Yadav; Lal Dhar S. Yadav; Rana Krishna Pal Singh

doi:10.1055/s-0037-1610264

Synlett, Table of Contents

Synlett 2018; 29(17): 2306-2310
DOI: 10.1055/s-0037-1610264

letter

K₂S₂O₈-Mediated Arylmethylation of Indoles with Tertiary Amines via sp³ C–H Oxidation in Water

Authors

Manjula Singh

^aGreen Synthesis Electrochemical laboratory, Department of Chemistry, University of Allahabad, Allahabad 211002, India
Arvind K. Yadav

^bGreen Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad 211002, India Email: ldsyadav@hotmail.com
Lal Dhar S. Yadav*

^bGreen Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad 211002, India Email: ldsyadav@hotmail.com
Rana Krishna Pal Singh*

^aGreen Synthesis Electrochemical laboratory, Department of Chemistry, University of Allahabad, Allahabad 211002, India

Abstract

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Abstract

A transition-metal- and catalyst-free, highly efficient synthesis of 3-arylmethylindoles has been achieved using tertiary amines as both methylene (-CH₂-) transfer and arylmethylation agents and K₂S₂O₈ as a convenient oxidant. The key feature of this protocol is the utilisation of K₂S₂O₈ as an inexpensive and easy to handle radical surrogate that can effectively promote the reaction, leading to the formation of C(sp²)–C(sp³)–C(sp²) bonds via sp³ C–H bond oxidation in water at room temperature in a one-pot procedure.

Key words

alkylation - indoles - tertiary amines - heterocycles - K₂S₂O₈ - radical oxidation

Full Text

References

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15 General procedure for the synthesis of 3-arylmethylindoles 3: A mixture of N,N-dimethylaniline 1 (2.0 mmol), indole 2 (1.0 mmol), K₂S₂O₈ (1.5 equiv), and CH₃CN (3 mL) was taken in a flask and stirred at r.t. for 2–4 h (Scheme 2). After completion of the reaction (monitored by TLC), water (5 mL) was added and the mixture was extracted with ethyl acetate (3 × 5 mL). The combined organic phase was dried over anhydrous Na₂SO₄, filtered, and evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography using a mixture of hexane/ethyl acetate (4:1) as eluent to afford an analytically pure sample of product 3. Compound 3a [see ref. 8]: ¹H NMR (400 MHz, CDCl₃): δ = 7.93 (s, 1 H), 7.52 (d, J = 7.9 Hz, 1 H), 7.34 (d, J = 8.1 Hz, 1 H), 7.14 (m, 3 H), 7.06 (m, 1 H), 6.85 (s, 1 H), 6.71 (d, J = 8.4 Hz, 2 H), 4.04 (s, 2 H), 2.93 (s, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 149.1, 136.6, 129.7, 129.3, 127.6, 122.1, 121.9, 120.0, 119.3, 116.7, 113.1, 111.0, 41.1, 30.6. HRMS (EI): m/z calcd for C₁₇H₁₈N₂: 250.1470; found: 250.1473.
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Supplementary Material

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