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Synlett 2020; 31(19): 1947-1952
DOI: 10.1055/s-0040-1707280
DOI: 10.1055/s-0040-1707280
letter
Integrated Synthesis of Thienyl Thioethers and Thieno[3,2-b]thiophenes via 1-Benzothiophen-3(2H)-ones
This work was supported in part by JSPS KAKENHI grants numbers JP16K05695, JP16K05777, JP19K05477, JP19K05478, and JP18H04455 in Middle Molecular Strategy, and by the Okayama Foundation for Science and Technology.
Abstract
A one-pot procedure for the synthesis of thienyl thioethers is described. Several thienyl thioethers were synthesized by a TfOH-promoted Friedel–Crafts-type cyclization, a subsequent nucleophilic attack by an arenethiol, and dehydration. This protocol was successfully applied to the synthesis of thienoacene derivatives by using a Pd-catalyzed dehydrogenative cyclization.
Key words
thienyl thioethers - thioetherification - one-pot synthesis - metal-free - halide-free - thienoacenesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707280.
- Supporting Information
Publication History
Received: 20 January 2020
Accepted after revision: 05 August 2020
Article published online:
21 September 2020
© 2020. Thieme. All rights reserved
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12 Further details of the base optimizations, see SI, Table S6.
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13
3-(4-Tolylsulfanyl)-1-benzothiophene (3a): One-Pot Synthesis; Typical Procedure
TfOH (0.136 mL, 231 mg, 1.54 mmol) was added dropwise to a solution of (phenylsulfanyl)acetic acid (1a; 33.6 mg, 0.20 mmol) in anhyd DCE (0.3 mL), and the resulting mixture was stirred at 40 °C for 3 h then cooled to 0 °C. 4-Methylbenzenethiol (24.8 mg, 0.20 mmol) and 2,6-lutidine (0.18 mL, 1.5 mmol) were added, and the mixture was stirred at 80 °C for 18 h then cooled to r.t. The reaction was quenched with sat. aq NaHCO3 (3 mL), and the mixture was extracted with CHCl3 (3 × 5 mL). The combined organic phase was dried (MgSO4), filtered, and concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, hexane) to give a colorless liquid; yield: 32.3 mg (0.13 mmol, 63%).IR (neat): 3096, 3021, 1595, 1254, 1016 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.28 (s, 3 H), 7.03 (d, J = 8.4 Hz, 2 H), 7.11 (d, J = 8.4 Hz, 2 H), 7.35–7.40 (m, 2 H), 7.62 (s, 1 H), 7.78–7.83 (m, 1 H), 7.86–7.90 (m, 1 H). 13C NMR (100 MHz, CDCl3): δ = 20.9, 122.9, 123.0, 124.7, 124.9, 125.0, 128.4, 129.8, 130.8, 132.5, 136.0, 138.8, 140.0.
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17 The structure of 4o was confirmed by X-ray crystal structure analysis. CCDC 1961314 contains the supplementary crystallographic data for compound 4o. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
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18 For details, see SI.
For representative examples of transition-metal-catalyzed dehydrogenative C–S coupling reactions, see:
For electrochemical C–S coupling reactions, see:
For light-driven C–S coupling reactions, see:
For representative examples, see: