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Synlett 2025; 36(08): 1039-1043
DOI: 10.1055/a-2463-5168
DOI: 10.1055/a-2463-5168
letter
One-Pot, Three-Component Coupling Synthesis of [(Benzothiazol-2-ylamino)(aryl)methyl]isoquinolinols under Catalyst- and Solvent-Free Conditions
Alluhaibi, M. S. and Hawsawi, M. B. are grateful to the Department of Chemistry, Faculty of Science, Umm Al-Qura University, Makkah 21955, Saudi Arabia, for their continuous support for this work. Gandhamsetty, N. is thankful for financial assistance from LNC PHARMARIX, Hyderabad, India.
Abstract
A one-pot, three-component coupling procedure has been developed for the synthesis of [(benzothiazol-2-ylamino)(aryl)methyl]isoquinolinols via the reaction of hydroxyisoquinolines, aryl/heteroaryl/aliphatic aldehydes with 2-aminobenzothiazoles under catalyst- and solvent-free conditions. The developed 2′-aminobenzothiazolomethylation procedure is suitable to execute even on a gram scale and has a broad scope. The 2′-aminobenzothiazolomethylated products (Betti bases) were formed through the initial nucleophilic C-attack of hydroxyisoquinolines on aldehydes to generate the ortho-quinone methide (o-QM) as an intermediate, followed by 1,4-aza-Michael addition of 2-aminobenzothiazoles. Betti bases have significance in medicinal chemistry due to their wide range of pharmacological applications and they are useful ligands and catalysts in asymmetric synthesis.
Key words
catalyst-free - solvent-free - aryl/heteroaryl/aliphatic aldehydes - three-component coupling - hydroxyisoquinolines - 2-aminobenzothiazoles - [(Benzothiazol-2-ylamino)(aryl)methyl]isoquinolinolsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2463-5168.
- Supporting Information
Publication History
Received: 29 September 2024
Accepted after revision: 07 November 2024
Accepted Manuscript online:
07 November 2024
Article published online:
06 December 2024
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- 21 General Procedure 1: Synthesis of 5- and 8-[(Benzothiazol-2-ylamino)(aryl)methyl]isoquinolinols (Tables 1–3, and Schemes 2 and 3): To a 10 mL round-bottom flask, aldehyde (1.1 mmol), powdered isoquinolin-7-ol or isoquinolin-6-ol (1.0 mmol), and 2-aminobenzothiazole (1.0 mmol) were added and the components were mixed well at 20–30 °C under nitrogen. The resulting reaction mixture was introduced to a pre-heated oil bath at 140 °C for the indicated time (Tables 1–3, and Schemes 2 and 3). Upon completion of the reaction, as indicated by TLC (50% ethyl acetate in hexanes), the reaction mixture was allowed to cool to room temperature. The solid crude reaction mixture was dissolved in methanol and dichloromethane, concentrated under reduced pressure at below 45 °C, and then crystallized with isopropyl alcohol (2 × 3 mL) and diisopropyl ether (3 mL) to afford the corresponding pure products.General Procedure 2: Synthesis of 5h (Table [3]): To a 10 mL round-bottom flask, pyridine-3-carbaldehyde (1.1 mmol), powdered isoquinolin-6-ol (1.0 mmol), and 2-aminobenzothiazole (1.0 mmol) were added and the components were mixed well at 20–30 °C under nitrogen. The resulting reaction mixture was then introduced to a pre-heated oil bath at 140 °C for the indicated time (Table 3). Upon completion of the reaction, as indicated by TLC (50% ethyl acetate in hexanes), the reaction mixture was allowed to cool to 20–30 °C. The crude reaction mixture was dissolved in methanol and dichloromethane then concentrated under reduced pressure at below 45 °C. The resulting residue was purified by silica gel (60-120 mesh) column chromatography with ethyl acetate/hexanes to afford pure product 5h (Table 3).