Thiolate-Protected Au₂₅(SC₂H₄Ph)₁₈ Nanoclusters as a Catalyst for Intermolecular Hydroamination of Terminal Alkynes

Abstract

Au₂₅(SC₂H₄Ph)₁₈ nanoclusters have high catalytic activity for hydroamination of terminal alkynes. This reaction proceeds under O₂ or air. The presence of molecular oxygen has a profound effect on the Au₂₅(SC₂H₄Ph)₁₈ reactivity. The catalysts can be separated from the mixture after the reaction and reused.

Key words

hydroamination - gold nanocluster - imines - gold catalyst - reusing catalyst

• Reference and Notes

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• 18 Preparation of the Au₂₅(SC₂H₄Ph)₁₈ Catalyst The Au₂₅(SC₂H₄Ph)₁₈ nanoclusters were synthesized according to a previously reported method.²⁰ HAuCl₄·4H₂O (2 mmol, 0.8 g) was dissolved in 150 ml tetrahydrofuran (THF) solution containing tetraoctylammonium bromide (2.4 mmol, 1.3 g) at room temperature. After stirring for 15 min, 2-phenylethanethiol (10 mmol, 1.4 g) was added, and the solution was stirred for 15 min 2 h. A cold aqueous solution (25 ml) containing NaBH₄ (20 mmol, 0.8 g) was then rapidly added to the solution, and the solution was then stirred at room temperature. After 15 h, the THF solvent was evaporated, and the remaining red brown powder was washed with methanol to remove excess thiol and other byproducts. The Au₂₅(SC₂H₄Ph)₁₈ clusters were extracted from the dried sample using acetonitrile.
• 19 General Procedure and the Analytical Data of some Typical Compounds The reaction of aniline (1a) with phenylacetylene (2a) was performed as follows. The prepared 1 mM Au₂₅(SC₂H₄Ph)₁₈nanocluster solution in toluene (0.5 mL) was added to a Schlenk flask and the solvent was evaporated. Then, 1a (0.5 mmol, 47 mg) and 2a (1.5 mmol, 153 mg) were added, and the solution was stirred for 24 h at 70 °C under O₂ (balloon). The chemical yield of imine 3a was determined by integrating the ¹H NMR spectrum with respect to an internal standard (1,3,5-trimethoxybenzene). Compound 3a was isolated by column chromatography (25 μm silica gel, n-hexane/ethyl acetate = 99:1). The yield was 63% (61 mg). 3a N-(1-Phenylethylidene)benzenamine Yellow solid; mp 40–41 °C. ¹H NMR (400 MHz CDCl₃): δ = 7.98–7.96 (2 H, m), 7.45–7.44 (3 H, m), 7.34 (2 H, t, J = 7.7 Hz), 7.08 (1 H, t, J = 7.2 Hz), 6.79 (2 H, d, J = 7.9 Hz), 2.22 (3 H, s); ¹³C NMR (100 MHz CDCl₃): δ = 165.48 (C), 151.65 (C), 139.42 (C), 130.46 (CH), 128.94 (CH), 128.36 (CH), 127.14 (CH), 123.20 (CH), 119.36 (CH), 17.38 (CH₃). GC-MS (EI): m/z (relative intensity) = 195 (53) [M]⁺, 180 (100), 118 (12). 3b N-(1-Phenylethylidene)-1-naphthalenamine Yellow solid; mp 85–86 °C. ¹H NMR (400 MHz CDCl₃) δ = 8.12–8.10 (2 H, m), 7.84–7.77 (2 H, m), 7.60–7.40 (7 H, m), 6.78 (1 H, d, J = 7.2 Hz), 2.19 (3 H, s). ¹³C NMR (400 MHz CDCl₃): δ = 166.42 (C), 147.93 (C), 139.20 (C), 134.15 (C), 130.64 (CH), 128.43 (CH), 127.94 (CH), 127.28 (CH), 126.08 (CH), 125.90 (C), 125.88 (CH), 125.37 (CH), 123.55 (CH), 123.21 (CH), 113.44 (CH), 17.66 (CH₃); GC-MS (EI) m/z (relative intensity) = 246 (12), 245 (62) [M]⁺, 231 (20), 230 (100), 128 (6), 127 (53).
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