Synlett 2022; 33(01): 57-61 DOI: 10.1055/a-1661-3152
Suzuki–Miyaura Cross-Coupling Reaction with Potassium Aryltrifluoroborate in Pure Water Using Recyclable Nanoparticle Catalyst
Misa Kawase
a
Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan
,
Kyosuke Matsuoka
a
Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan
,
Tsutomu Shinagawa
b
Osaka Municipal Technical Research Institute, 1-6-50 Morinomiya, Joto, Osaka, 536-8553, Japan
,
Go Hamasaka
c
Institute for Molecular Science (IMS), Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan
,
Yasuhiro Uozumi
c
Institute for Molecular Science (IMS), Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan
,
Osamu Shimomura
a
Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan
,
a
Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan
› Author Affiliations The authors are grateful to the Nanomaterials and Microdevices Research Center (NMRC) of OIT for financial and instrumental supports. This work was supported by the Joint Studies Program of the Institute for Molecular Science.
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
Supporting Information
Supporting information for this article is available online at https://doi.org/10.1055/a-1661-3152.
Supporting Information
Publication History
Received: 26 August 2021
Accepted after revision: 04 October 2021
Accepted Manuscript online: 04 October 2021
Article published online: 26 October 2021
© 2021. Thieme. All rights reserved
Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
References and Notes
1
Vedejs E,
Chapman RW,
Fields SC,
Lin S,
Schrimpf MR.
J. Org. Chem. 1995; 60: 3020
For recent studies on the Suzuki coupling reaction with potassium aryltrifluoroborate, see:
2a
Li X,
Liu C,
Wang L,
Ye Q,
Jin X,
Jin Z.
Org. Biomol. Chem. 2018; 16: 8719
2b
Barbeiro CS,
Vasconcelos SN. S,
de Oliveira IM,
Zukerman-Schpector J,
Caracelli I,
Maganhi SH,
Stefani HA.
ChemistrySelect 2017; 2: 8173
2c
Gómez-Martínez M,
Buxaderas E,
Pastor IM,
Alonso DA.
J. Mol. Catal. A: Chem. 2015; 404: 1
2d
Liu C,
Li X,
Gao Z,
Wang X,
Jin Z.
Tetrahedron 2015; 71: 3954
2e
Liu C,
Li X,
Wang X,
Jin Z.
Catal. Commun. 2015; 69: 81
2f
Yuen OY,
Wong SM,
Chan KF,
So CM,
Kwong FY. A.
Synthesis 2014; 46: 2826
2g
Liu L,
Dong Y,
Pang B,
Ma J.
J. Org. Chem. 2014; 79: 7193
2h
Liu L,
Dong Y,
Tang N.
Green Chem. 2014; 16: 2185
2i
Bratt E,
Verho O,
Johansson MJ,
Bäckvall J.-E.
J. Org. Chem. 2014; 79: 3946
For recent studies on the Suzuki-type coupling reaction with potassium aryltrifluoroborate, see:
3a
Li X,
Ma Y,
Hu Q,
Jiang B,
Wu Q,
Yuan Z.
Catal. Commun. 2018; 117: 57
3b
Wang G,
Meng M,
Deng L,
Cheng K,
Qi C.
Appl. Organomet. Chem. 2018; 32: e4203
3c
Chang S,
Sun YB,
Zhang XR,
Dong LL,
Zhu HY,
Lai HW,
Wang D.
Appl. Organomet. Chem. 2018; 32: e3970
3d
Wei Z,
Xue D,
Zhang H,
Guan J.
Appl. Organomet. Chem. 2016; 30: 767
3e
Singh PP,
Aithagani SK,
Yadav M,
Singh VP,
Vishwakarma RA.
J. Org. Chem. 2013; 78: 2639
3f
Wang Z.-Y,
Ma Q.-N,
Li R.-H,
Shao L.-X.
Org. Biomol. Chem. 2013; 11: 7899
4
Yuan Y.-C,
Bruneau C,
Roisnel T,
Gramage-Doria R.
J. Org. Chem. 2019; 84: 12893
5
Phillips D,
Hewitt JF. M,
France DJ.
ACS Omega 2018; 3: 8451
6a
Ghosh P,
Ganguly B,
Perl E,
Das S.
Tetrahedron Lett. 2017; 58: 2751
6b
Zhao H,
Han W.
Eur. J. Org. Chem. 2016; 4279
6c
Wang X,
Liu M,
Xu L,
Wang Q,
Chen J,
Ding J,
Wu H.
J. Org. Chem. 2013; 78: 5273
7
Miao J,
Fang P,
Jagdeep S,
Ge H.
Org. Chem. Front. 2016; 3: 243
8
Rizwan K,
Karakaya I,
Heitz D,
Zubair M,
Rasool N,
Molander GA.
Tetrahedron Lett. 2015; 56: 6839
9
Paymode DJ,
Ramana CV.
J. Org. Chem. 2015; 80: 11551
10
Kuriyama M,
Shimazawa R,
Enomoto T,
Shirai R.
J. Org. Chem. 2008; 73: 6939
11a
Cortes-Clerget M,
Yu J,
Kincaid JR. A,
Walde P,
Gallou F,
Lipshutz BH.
Chem. Sci. 2021; 12: 4237
11b
Ansari TN,
Jasinski JB,
Leahy DK,
Handa S.
JACS Au 2021; 1: 308
11c
Hazra S,
Kaur G,
Handa S.
ACS Sustainable Chem. Eng. 2021; 9: 5513
11d
Kitanosono T,
Kobayashi S.
Chem. Eur. J. 2020; 26: 9408
12 The recyclability of Pd/PVP has been reported. See:
Wang L,
Li P.-H.
Chin. J. Chem. 2006; 24: 770
13a
Ohtaka A.
Curr. Org. Chem. 2019; 23: 689
13b
Osako T,
Ohtaka A,
Uozumi Y.
Catalyst Immobilization
.
Benaglia M,
Puglisi A.
Wiley-VCH; Weinheim: 2019: 325-368
14
Ohtaka A,
Teratani T,
Fujii R,
Ikeshita K,
Kawashima T,
Tatsumi K,
Shimomura O,
Nomura R.
J. Org. Chem. 2011; 76: 4052
15
Preparation of PS-PdONPs Pd(OAc)2 (8.4 mg, 37.5 μmol), polystyrene (11.3 mg, 0.139 mmol of PS unit), and aqueous K2 CO3 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).
16
Ohtaka A,
Okagaki T,
Hamasaka G,
Uozumi Y,
Shinagawa T,
Shimomura O,
Nomura R.
Catalysts 2015; 5: 106
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.
20a
Anton DR,
Crabtree RH.
Organometallics 1983; 2: 855
20b
Consorti CS,
Flores FR,
Dupont J.
J. Am. Chem. Soc. 2005; 127: 12054
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% (1st run), TON is 1/0.005 x 0.84 = 168. Thus, total TON is 1056 (2nd -6th 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 H2 O (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 1 H 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%). 1 H 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). 13 C 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%). 1 H 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). 13 C 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%). 1 H 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). 13 C 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%). 1 H 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). 13 C 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%). 1 H 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). 13 C 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%). 1 H 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). 13 C 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%). 1 H NMR (400 MHz, CDCl3 ): δ = 7.25–7.20 (m, 8 H), 2.40 (s, 3 H), 2.28 (s, 3 H). 13 C 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%). 1 H 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). 13 C 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%). 1 H 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). 13 C 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%). 1 H 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). 13 C 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%). 1 H 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). 13 C 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%). 1 H 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). 13 C 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%). 1 H NMR (400 MHz, CDCl3 ): δ = 7.42–7.21 (m, 9 H), 2.23 (s, 3 H). 13 C 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%). 1 H 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). 13 C 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%). 1 H 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). 13 C 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.