Fluoride-Free Hiyama Coupling Reaction Catalyzed by Linear Polystyrene-Stabilized PdO Nanoparticles in Water: Specific Reactivity of PdO Nanoparticles over Pd Nanoparticles

Abstract

Linear polystyrene-stabilized PdO nanoparticles (PS-PdONPs) exhibited high catalytic activity for fluoride-free Hiyama coupling reaction of aryltrimethoxysilanes with a variety of bromoarenes under air in water. In contrast, no desired coupling product was obtained from the Hiyama coupling reaction using linear polystyrene-stabilized Pd nanoparticles (PS-PdNPs) as a catalyst. The different reactivities of PdONPs and PdNPs will be discussed.

Key words

polystyrene - PdO nanoparticles - Pd nanoparticles - Hiyama coupling reaction - water

• References and Notes

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• 8 General Procedure for Hiyama Coupling Reaction (Table 1): To a screw-capped vial with a stirring bar were added 4-bromotoluene (86.4 mg, 0.5 mmol), phenyltrimethoxysilane (152 mg, 0.75 mmol), PS-PdONPs (2.9 mg, 1.5 mol% of Pd), TBAC (142 mg, 0.5 mmol), and aq NaOH solution (1.5 M, 1 mL). After stirring at 80 °C for 3 h, the reaction mixture was cooled to r.t. by immediately immersing the vial in H₂O (ca. 20 °C) for about 10 min. After separating the catalyst and the aqueous phase by centrifugation, the aqueous phase was decanted. The recovered catalyst was washed with H₂O (5 × 3.0 mL) and Et₂O (5 × 3.0 mL), which were then added to the aqueous phase. The aqueous phase was extracted eight times with Et₂O. The combined organic extracts were dried over MgSO₄ and concentrated under reduced pressure. The product was analyzed by ¹H NMR. The recovered catalyst was dried in vacuo and reused. Furthermore, the amount of Pd metal in the aqueous phase determined by ICP-AES analysis was <0.1 ppm. 4-Methylbiphenyl: ¹H NMR (CDCl₃): δ = 7.55–7.60 (m, 2 H), 7.47–7.50 (m, 2 H), 7.39–7.43 (m, 2 H), 7.29–7.33 (m, 1 H), 7.20–7.25 (m, 2 H), 2.38 (s, 3 H). ¹³C NMR (CDCl₃): δ = 141.1, 138.3, 136.9, 129.4, 128.7, 128.7, 126.9, 21.1. CAS registry number: 644-08-6. 4-Methoxybiphenyl: ¹H NMR (CDCl₃): δ = 7.51–7.58 (m, 4 H), 7.42 (t, J = 7.6 Hz, 2 H), 7.31 (t, J = 7.6 Hz, 1 H), 6.98 (d, J = 8.7 Hz, 2 H), 3.85 (s, 3 H). ¹³C NMR (CDCl₃): δ = 159.1, 140.7, 133.7, 128.6, 128.0, 126.6, 126.6, 114.2, 55.3. CAS registry number: 613-37-6. 4-Nitrobiphenyl: ¹H NMR (CDCl₃): δ = 8.30 (d, J = 8.4 Hz, 2 H), 7.74 (d, J = 8.4 Hz, 2 H), 7.43–7.62 (m, 5 H). ¹³C NMR (CDCl₃): δ = 147.7, 147.2, 138.9, 129.3, 129.1, 127.8, 127.5, 124.2. CAS registry number: 92-93-3. 2-Methylbiphenyl: ¹H NMR (CDCl₃): δ = 7.21–7.42 (m, 9 H), 2.23 (s, 3 H). ¹³C NMR (CDCl₃): δ = 142.3, 135.8, 131.3, 129.7, 129.3, 128.5, 128.4, 128.2, 127.6, 125.3, 20.5. CAS registry number: 643-58-3. 1-Phenylnaphthalene: ¹H NMR (CDCl₃): δ = 7.81–7.90 (m, 3 H), 7.36–7.51 (m, 9 H). ¹³C NMR (CDCl₃): δ = 140.9, 140.4, 134.0, 131.8, 130.2, 128.4, 127.7, 127.3, 127.0, 126.1, 125.8, 125.4. CAS registry number: 605-02-7. 4,4′-Dimethylbiphenyl: ¹H NMR (CDCl₃): δ = 7.47 (d, J = 8.1 Hz, 4 H), 7.23 (d, J = 8.1 Hz, 4 H), 2.38 (s, 6 H). ¹³C NMR (CDCl₃): δ = 138.2, 136.7, 129.4, 126.8, 21.1. CAS registry number: 613-33-2.
• 9a Preparation of Polystyrene-Stabilized PdO Nanoparticles (PS-PdONPs): PS-PdONPs was prepared according to our previous publication.^9b To a screw-capped vial with a stirring bar were added polystyrene (9.0 mg, 85 μmol of styrene unit), Pd(OAc)₂ (5.5 mg, 25 mol), and 1.5 M aqueous K₂CO₃ solution (3 mL). After stirring at 90 °C for 1 h, the reaction mixture was cooled to r.t. by immediately immersing the vial in H₂O for approximately 10 min. After separating the catalyst and the aqueous phase through centrifugation, the aqueous phase was decanted. The catalyst was washed with H₂O (5 × 1.0 mL) and MeOH (5 × 1.0 mL).
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• 10 Preparation of Polystyrene-Stabilized Pd Nanoparticles (PS-PdNPs, size of NPs = 1.7 ± 0.2 nm): PS-PdNPs was prepared according to our previous publication.^9b To a screw-capped vial with a stirring bar were added polystyrene (1.8 mg, 17 μmol of styrene unit), Pd(OAc)₂ (1.0 mg, 5 μmol), phenylboronic acid (9.1 mg, 0.75 mmol), and H₂O (1 mL). After stirring at 90 °C for 1 h, the aqueous solution was decanted. Subsequently, the polystyrene-stabilized Pd nanoparticles were washed with H₂O (5 × 1.0 mL) and acetone (5 × 1.0 mL).
• 11 The catalytic activity for the Hiyama coupling reaction increased with an increase in the size of PdNPs. Indeed, when the Hiyama coupling reaction of 4-bromotoluene with phenyltrimethoxysilane was performed with PS-PdNPs (>5 nm) prepared by benzyl alcohol, 4-methylbiphenyl and 4,4′-dimethylbiphenyl were obtained in 36% and 9% yields, respectively.
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• 13 No Ullmann coupling product was obtained in the absence of MeOH or on using PS-PdONPs as a catalyst.
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