Suzuki–Miyaura Cross-Coupling Reaction with Potassium Aryltrifluoroborate in Pure Water Using Recyclable Nanoparticle Catalyst

Misa Kawase; Kyosuke Matsuoka; Tsutomu Shinagawa; Go Hamasaka; Yasuhiro Uozumi; Osamu Shimomura; Atsushi Ohtaka

doi:10.1055/a-1661-3152

Synlett, Table of Contents

Synlett 2022; 33(01): 57-61
DOI: 10.1055/a-1661-3152

letter

Suzuki–Miyaura Cross-Coupling Reaction with Potassium Aryltrifluoroborate in Pure Water Using Recyclable Nanoparticle Catalyst

Misa Kawase

^aDepartment of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan

,

Kyosuke Matsuoka

^aDepartment of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan

,

Tsutomu Shinagawa

^bOsaka Municipal Technical Research Institute, 1-6-50 Morinomiya, Joto, Osaka, 536-8553, Japan

,

Go Hamasaka

^cInstitute for Molecular Science (IMS), Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan

,

Yasuhiro Uozumi

^cInstitute for Molecular Science (IMS), Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan

,

Osamu Shimomura

^aDepartment of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan

,

Atsushi Ohtaka ∗

^aDepartment of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan

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Abstract

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Abstract

This paper describes the Suzuki–Miyaura cross-coupling reaction of aryl bromides with potassium aryltrifluoroborates in water catalyzed by linear polystyrene-stabilized PdO nanoparticles (PS-PdONPs). The reaction of aryl bromides having electron-withdrawing groups or electron-donating groups took place smoothly to give the corresponding coupling product in high yields. The catalyst recycles five times without significant loss of catalytic activity although a little bit increase in size of PdNPs was observed after the reaction.

Key words

Suzuki–Miyaura cross-coupling - potassium aryltrifuoroborate - nanoparticles - water - recycling

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References

References and Notes
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15 Preparation of PS-PdONPsPd(OAc)₂ (8.4 mg, 37.5 μmol), polystyrene (11.3 mg, 0.139 mmol of PS unit), and aqueous K₂CO₃ solution (1.5 mol/L, 3 mL) were added to a screw-capped vial (no. 1, Maruemu Co., Osaka, Japan) with a stirring bar. After stirring (1350 rpm) at 90 °C for 5 h, the reaction mixture was cooled to room temperature. After separating the solid and the aqueous solution by centrifugation, the aqueous phase was decanted. PS-PdONPs (13.3 mg) was obtained after washing with water (3 × 3.0 mL), methanol (3 × 3.0 mL), and diethyl ether (3 × 3.0 mL).
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17 When the reaction of 2-bromopyridine with 4-methylphenylboronic acid was performed under the same reaction conditions, the yield of coupling product was 16%.
18 Mulliken charge population on ipso-carbon in PhBF₃ ^– (–0.596) calculated using DFT method (B3LYP/6-31+G** level of theory) is more positive than that in PhB(OH)₃ ^– (–0.950), indicating the aryl group in PhBF₃ ^– is less nucleophilic than that in PhB(OH)₃ ^–.
19 When the aqueous phase was reused for the next catalytic reaction after removal of product and catalyst, 7% of coupling product was obtained. This result is indicating the lower amount of Pd than the detectable level in ICP analysis existed in the aqueous phase.

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21 When the aqueous phase was analyzed by ICP-OES after heating the mixture of 2-bromothiophene and PS-PdONPs under the reaction conditions, 1.0% of Pd species based on the total amount of Pd in PS-PdONPs was detected.
22 The reaction in which metal leaching is considered to occur after the oxidative addition of aryl halides to metal nanoparticles will take place through the similar ‘on water then in water’ route. See: Gnad C, Abram A, Urstöger A, Weigl F, Schuster M, Köhler K. ACS Catal. 2020; 10: 6030
23 The ‘in water then on water’ route has been advocated in Hiyama coupling reaction. See: Sakon A, Ii R, Hamasaka G, Uozumi Y, Shinagawa T, Shimomura O, Nomura R, Ohtaka A. Organometallics 2017; 36: 1618
24 With a 0.5 mol% catalyst and a yield of 84% (1^st run), TON is 1/0.005 x 0.84 = 168. Thus, total TON is 1056 (2^nd-6^th runs: 182, 188, 176, 172, and 170).
25 Typical Procedure for the Suzuki–Miyaura Cross-Coupling Reaction PS-PdONPs (1.0 mg, 0.5 mol% of Pd based on bromobenzene), potassium p-tolyltrifluoroborate (99 mg, 0.5 mmol), bromobenzene (78.5 mg, 0.5 mmol), cesium carbonate (488.7 mg, 1.5 mmol), and 1.0 mL water were added to a screw-capped vial (no. 02, Maruemu Co., Osaka, Japan) with stirring bar. After stirring at 90 °C for 2 h, the reaction mixture was cooled to room temperature. After separating the catalyst and the aqueous phase by centrifugation, the aqueous phase was decanted. Recovered catalyst was washed with H₂O (5 × 3.0 mL) and diethyl ether (5 × 3.0 mL), which were then added to the aqueous phase. The aqueous phase was extracted eight times with diethyl ether. The combined organic extracts were dried over MgSO₄ and concentrated under reduced pressure. The product was analyzed by ¹H NMR spectroscopy. The recovered catalyst was dried in vacuo and reused. The crude material was purified with silica gel column chromatography (hexane) to give 4-methylbiphenyl in 80% yield. (Note: The yields below are isolated yields while the yields in Table 2 are NMR yields). 4-Methylbiphenyl White solid (67 mg, 80%). ¹H NMR (400 MHz, CDCl₃): δ = 7.60–7.55 (m, 2 H), 7.50–7.47 (m, 2 H), 7.43–7.39 (m, 2 H), 7.33–7.29 (m, 1 H), 7.25–7.20 (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. 4,4′-Dimethylbiphenyl White solid (80 mg, 88%). ¹H NMR (400 MHz, 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. 4-Methoxy-4′-methylbiphenyl White solid (84 mg, 85%). ¹H NMR (400 MHz, CDCl₃): δ = 7.51 (d, J = 9.0 Hz, 2 H), 7.45 (d, J = 8.1 Hz, 2 H), 7.22 (d, J = 8.1 Hz, 2 H), 6.96 (d, J = 9.0 Hz, 2 H), 3.84 (s, 3 H), 2.38 (s, 3 H). ¹³C NMR (CDCl₃): δ = 158.9, 137.9, 136.3, 133.7, 129.4, 127.9, 126.6, 114.2, 55.3, 21.0. CAS registry number: 53040-92-9. 4-Acetyl-4′-methylbiphenyl White solid (92 mg, 88%). ¹H NMR (400 MHz, CDCl₃): δ = 8.02 (d, J = 8.7 Hz, 2 H), 7.67 (d, J = 8.7 Hz, 2 H), 7.53 (d, J = 8.4 Hz, 2 H), 7.27 (d, J = 8.4 Hz, 2 H), 2.63 (s, 3 H), 2.41 (s, 3 H). ¹³C NMR (CDCl₃): δ = 197.8, 145.7, 138.2, 136.9, 135.5, 129.7, 128.9, 127.1, 126.9, 26.6, 21.2. CAS registry number: 5748-38-9. 4-Methyl-4′-(trifluoromethyl)biphenyl White solid (106 mg, 90%). ¹H NMR (400 MHz, CDCl₃): δ = 7.67 (m, 4 H), 7.50 (d, J = 8.4 Hz, 2 H), 7.28 (d, J = 8.4 Hz, 2 H), 2.41 (s, 3 H). ¹³C NMR (CDCl₃): δ = 144.6, 138.1, 136.8, 129.7, 129.2 (q, J = 32.3 Hz), 127.2, 127.1, 125.6 (q, J = 4.2 Hz), 124.3 (q, J = 271.7 Hz), 21.1. CAS registry number: 97067-18-0. 4-Methyl-4′-nitrobiphenyl Yellow solid (83 mg, 78%). ¹H NMR (400 MHz, CDCl₃): δ = 8.28 (d, J = 8.3 Hz, 2 H), 7.72 (d, J = 8.3 Hz, 2 H), 7.53 (d, J = 8.3 Hz, 2 H), 7.30 (d, J = 8.3 Hz, 2 H), 2.43 (s, 3 H). ¹³C NMR (CDCl₃): δ = 147.5, 146.7, 139.0, 135.7, 130.2, 127.5, 127.0, 124.0, 21.1. CAS registry number: 2143-88-6. 2,4′-Dimethylbiphenyl White solid (62 mg, 68%). ¹H NMR (400 MHz, CDCl₃): δ = 7.25–7.20 (m, 8 H), 2.40 (s, 3 H), 2.28 (s, 3 H). ¹³C NMR (CDCl₃): δ = 141.8, 140.0, 136.4, 135.4, 130.2, 129.8, 129.0, 128.7, 127.0, 125.7, 21.27, 20.5. CAS registry number: 611-61-0. 2,4′,6-Trimethylbiphenyl Colorless oil (47 mg, 48%). ¹H NMR (400 MHz, CDCl₃): δ = 7.44 (d, J = 7.7 Hz, 2 H), 7.30–7.38 (m, 3 H), 7.25 (d, J = 8.0 Hz, 2 H), 2.61 (s, 3 H), 2.28 (s, 6 H). ¹³C NMR (CDCl₃): δ = 141.8, 138.0, 136.1, 129.0, 128.8, 126.8, 21.1, 20.8. CAS registry number: 76708-76-4. 1-(p-Tolyl)naphtharene White solid (55 mg, 50%). ¹H NMR (400 MHz, CDCl₃): δ = 8.04 (d, J = 8.5 Hz, 1 H), 8.00 (d, J = 8.0 Hz, 1 H), 7.94 (d, J = 8.5 Hz, 1 H), 7.64–7.45 (m, 6 H), 7.40 (d, J = 8.0 Hz, 2 H), 2.55 (s, 3 H). ¹³C NMR (CDCl₃): δ = 140.2, 137.8, 136.9, 133.8, 131.7, 129.8, 128.9, 128.3, 127.5, 126.1, 125.9, 125.4, 21.2. CAS registry number: 27331-34-6. 4-Methoxybiphenyl White solid (78 mg, 85%). ¹H NMR (400 MHz, CDCl₃): δ = 7.58–7.51 (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-Acetylbiphenyl White solid (67 mg, 68%). ¹H NMR (400 MHz, CDCl₃): δ = 8.03 (d, J = 8.4 Hz, 2 H), 7.68–7.62 (m, 4 H), 7.47–7.39 (m, 3 H), 2.63 (s, 3 H). ¹³C NMR (CDCl₃): δ = 198.0, 146.0, 140.1, 136.1, 132.9, 129.3, 129.2, 128.9, 127.5, 26.4. CAS registry number: 92-91-1. 4-Trifluoromethylbiphenyl White solid (106 mg, 95%). ¹H NMR (400 MHz, CDCl₃): δ = 7.76–7.68 (m, 4 H), 7.68–7.58 (m, 2 H), 7.51–7.38 (m, 3 H). ¹³C NMR (CDCl₃): δ = 144.7, 139.7, 129.3 (q, J = 32.3 Hz), 129.0, 128.2, 127.6, 127.4, 127.3, 125.6 (q, J = 3.2 Hz), 124.3 (q, J = 272.1 Hz). CAS registry number: 398-36-7. 2-Methylbiphenyl White solid (55 mg, 65%). ¹H NMR (400 MHz, CDCl₃): δ = 7.42–7.21 (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. 2-(p-Tolyl)thiophene White solid (45 mg, 52%). ¹H NMR (400 MHz, CDCl₃): δ = 7.48 (d, J = 8.2 Hz, 2 H), 7.23 (d, J = 3.6 Hz, 1 H), 7.19 (d, J = 5.0 Hz, 1 H), 7.15 (d, J = 8.2 Hz, 2 H), 7.06 (dd, J = 5.0, 3.6 Hz, 1 H), 2.32 (s, 3 H). ¹³C NMR (CDCl₃): δ = 144.6, 137.0, 131.7, 129.5, 127.9, 125.8, 124.2, 122.6, 21.2. CAS registry number: 16939-04-1. 2-(p-Tolyl)pyridine Pale yellow oil (69 mg, 81%). ¹H NMR (400 MHz, CDCl₃): δ = 8.66 (d, J = 4.8 Hz, 1 H), 7.88 (d, J = 8.4 Hz, 2 H), 7.75–7.69 (m, 2 H), 7.28 (d, J = 8.4 Hz, 2 H), 7.20 (td, J = 4.8, 2.0 Hz, 1 H), 2.41 (s, 3 H). ¹³C NMR (CDCl₃): δ = 157.6, 149.7, 139.0, 136.8, 136.7, 129.6, 126.9, 121.9, 120.4, 21.4. CAS registry number: 4467-06-5.

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