Indium(III)-Catalyzed Tandem Hydroamination–Hydroarylation of Naphthylamines with Phenylacetylenes

Abstract

A one-pot, three-component method for the synthesis of benzo-fused quinolines has been developed by tandem reaction between phenylacetylenes and naphthylamines. The first step of the reaction is hydroamination of the alkyne followed by a hydroarylation reaction to form the quinolines. Indium(III) trifluoromethanesulfonate was shown to be an efficient catalyst for the transformations, and the reaction proceeded in the absence of any other co-catalyst or additive to give the corresponding quinolines in good to excellent yields.

Key words

indium - alkynes - hydroamination - hydroarylation - domino reactions

• References and Notes


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• 16 Synthesis of 3a–i; General Procedure: 2-Naphthylamine (1 mmol), alkyne (4 mmol), and In(OTf)₃ (0.1 mmol) were heated at reflux in toluene (10 mL) for 10 h under air. Upon completion of the reaction (as indicated by TLC), the solvent was evaporated and the crude product mixture was dissolved in chloroform and purified by column chromatography (EtOAc–hexane, 15:85) to give pure 3. 2-Methyl-2,3-diphenyl-1,2-dihydrobenzo[f]quinoline (3a): Light-yellow liquid; ¹H NMR (300 MHz, CDCl₃): δ = 7.96 (d, J = 7.46 Hz, 3 H), 7.61 (m, 6 H), 7.28 (m, 5 H), 7.04 (m, 2 H), 5.82 (s, 1 H), 4.72 (s, 1 H), 2.59 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 148.1, 142.9, 142.7, 137.1, 137.0, 133.1, 130.6, 130.1, 128.8, 128.6, 128.3, 128.2, 127.0, 126.7, 126.0, 125.3, 124.9, 121.5, 117.2, 113.1, 55.8, 26.6. IR (CHCl₃): 3415, 1381, 1239, 755 cm^–1. GC-MS: m/z = 347 [M]⁺. Anal. Calcd for C₂₆H₂₁N: C, 89.88; H, 6.09; N, 4.03. Found: C, 89.98; H, 6.15; N, 4.01.