Special Edition Thieme Chemistry Journals Awardees 2022
CsOH-Promoted Regiospecific Sulfenylation, Selenylation, and Telluration of Indoles in H2O
Shitang Xu
a
State Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China
,
Rongnan Yi
a
State Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China
,
Chunling Zeng
a
State Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China
,
Yue Cui
a
State Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China
a
State Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China
c
Molecular Science and Biomedicine Laboratory (MBL), Hunan University, Changsha, Hunan, 410082, P. R. of China
,
Xinhua Xu
a
State Key Laboratory of Chemo/Biosensing and Chemometrics; College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. of China
,
Ningbo Li∗
b
Department of Chemistry, School of Basic Medical Sciences, Shanxi Medical University, Taiyuan 030001, P. R. of China
› Author AffiliationsThis work is supported by the National Key Research and Development Program of China (2018YFA0902300), the National Natural Science Foundation of China (No. 21802093 and No. 21273068), the Huxiang Young Talent Program from Hunan Province (2019RS2022), and the Science and Technology Project of Hunan Province (2019sk2201).
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
Supporting Information
Supporting information for this article is available online at https://doi.org/10.1055/a-1879-2521.
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22Typical 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+].
