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Synlett 2018; 29(20): 2693-2696
DOI: 10.1055/s-0037-1611023
letter
© Georg Thieme Verlag Stuttgart · New York

Base-Promoted Three-Component One-Pot Synthesis of 3- (Thiomethyl)indoles with Paraformaldehyde under Aqueous Conditions

Fuhong Xiao*
Key Laboratory for Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, P. R. of China   Email: fhxiao@xtu.edu.cn   Email: gjdeng@xtu.edu.cn
,
Shanshan Yuan
,
Huawen Huang
,
Guo-Jun Deng*
› Author Affiliations
We gratefully acknowledge the support for this work provided by the National Natural Science Foundation of China (21572194, 21502160). The project was supported by the Scientific Research Fund of Hunan Provincial Education Department (YB2016B024), the China Post­doctoral Science Foundation Funded Project (2015M572257), and ­Hunan Provincial Natural Science Foundation of China (16JJ3112).
Further Information

Publication History

Received: 09:08:2018

Accepted after revision: 24:09:2018

Publication Date:
17 October 2018 (online)

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Abstract

An ethylenediamine-promoted three-component synthesis of 3-(thiomethyl)indoles from indoles, thiophenols, and paraformaldehyde has been developed. Water is used as the green solvent in a simple and environmentally friendly procedure. Stable and low-toxicity paraformaldehyde is used as a carbon source.

Key words

metal-free - aqueous conditions - paraformaldehyde - multicomponent reaction - thiomethylation - thiomethylindoles

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611023.
  • Supporting Information
 

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  • 16 1-Methyl-3-{[(4-tolyl)thio]methyl}-1H-indole (3aa); Typical Procedure A 10 mL oven-dried reaction vessel was charged with 1-methyl-1H-indole (1a, 50 μL, 0.4 mmol), paraformaldehyde (24 mg, 0.8 mmol), 4-methylbenzenethiol (2a, 24.8 mg, 0.2 mmol). The vessel was sealed, and ethane-1,2-diamine (6.5 μL, 0.1 mmol) and H2O (0.5 mL) were added from a syringe. The resulting solution was stirred at 130 °C for 4 h. The volatiles were removed under vacuum, and the residue was purified by column chromatography [silica gel, PE–EtOAc ( 100:1)] to give a brown liquid; yield: 41.7 mg (78%). 1H NMR (400 MHz, CDCl3): δ = 7.67 (d, J = 7.9 Hz, 1 H), 7.28–7.20 (m, 4 H), 7.14–7.10 (m, 1 H), 7.08–7.06 (m, 2 H), 6.91 (s, 1 H), 4.30 (s, 2 H), 3.69 (s, 3 H), 2.30 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 137.0, 136.0, 133.6, 130.0, 129.5, 127.7, 127.2, 121.8, 119.2, 119.1, 110.2, 109.3, 32.66, 30.34, 21.00. HRMS (ESI): m/z [M + H]+ calcd for C17H18NS: 268.11545; found: 268.11554.