CsOH-Promoted Regiospecific Sulfenylation, Selenylation, and Telluration of Indoles in H2O

Shitang Xu; Rongnan Yi; Chunling Zeng; Yue Cui; Xue-Qiang Wang; Xinhua Xu; Ningbo Li

doi:10.1055/a-1879-2521

Synlett, Inhaltsverzeichnis

Synlett 2023; 34(02): 124-132
DOI: 10.1055/a-1879-2521

cluster

Special Edition Thieme Chemistry Journals Awardees 2022

CsOH-Promoted Regiospecific Sulfenylation, Selenylation, and Telluration of Indoles in H₂O

Shitang Xu

^aState Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China

,

Rongnan Yi

^aState Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China

,

Chunling Zeng

^aState Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China

,

Yue Cui

^aState Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China

,

Xue-Qiang Wang ∗

^aState Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China

^cMolecular Science and Biomedicine Laboratory (MBL), Hunan University, Changsha, Hunan, 410082, P. R. of China

,

Xinhua Xu

^aState Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China

,

Ningbo Li∗

^bDepartment of Chemistry, School of Basic Medical Sciences, Shanxi Medical University, Taiyuan 030001, P. R. of China

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Abstract

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Abstract

Various indole-containing compounds have shown impressive pharmaceutical activities against a variety of diseases. However, the functionalization of indoles usually relies on systems that use organic solvents, which do not meet the criteria for green and sustainable chemical development. To address this issue, regiospecific sulfenylation, selenylation, and telluration of indoles were developed using H₂O as solvent. The highly efficient chalcogenylation of indoles was achieved utilizing CsOH as a promoter, thus avoiding the use of expensive transition-metal catalysts. This newly developed protocol is characterized by its outstanding features including simple operation, mild conditions, wide substrate scope, excellent functional group tolerance, and recyclability, leading to the convenient synthesis of 3-chalcogenyl-indoles.

Key words

indole - regiospecific - chalcogenation - H₂O

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Referenzen

References and Notes

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22 Typical Procedure for the Synthesis of 3-(Phenylthio)-1H-indole Indole (0.5 mmol), diphenyl disulfide (0.25 mmol), CsOH·H₂O (0.75 mmol), and H₂O (0.2 mL) were added. Then the mixture was stirred at 70 °C, under air for 5 h. After the reaction finished, the mixture was extracted with ethyl acetate (3 × 3.0 mL). The upper layer of the organic phase is slowly drawn out with a syringe. The remaining trace water phase is used for the next cycle. The organic phase was dried over Na₂SO₄ and concentrated under vacuum. The residue was purified by flash chromatography on silica gel to afford give a white solid 3a;^18a 104.7 mg, 93% yield. ¹H NMR (400 MHz, CDCl₃): δ = 8.39 (s, 1 H), 7.61 (d, J= 7.6 Hz, 1 H), 7.46 (d, J= 2.4 Hz, 1 H), 7.42 (d, J= 8.4 Hz, 1 H), 7.28–7.24 (m, 1 H), 7.18–7.13 (m, 3 H), 7.10 (d, J = 7.6 Hz, 2 H), 7.06–7.03 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 139.3, 136.5, 130.7, 129.1, 128.7, 125.9, 124.8, 123.1, 120.9, 119.7, 111.6, 102.8. MS: m/z = 225.3 [M⁺].

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