Synlett 2016; 27(08): 1202-1206
DOI: 10.1055/s-0035-1560604
cluster
© Georg Thieme Verlag Stuttgart · New York

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

Atsushi Ohtaka*
a  Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan   Email: atsushi.otaka@oit.ac.jp
,
Takamasa Kotera
a  Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan   Email: atsushi.otaka@oit.ac.jp
,
Akira Sakon
a  Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan   Email: atsushi.otaka@oit.ac.jp
,
Kouhei Ueda
a  Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan   Email: atsushi.otaka@oit.ac.jp
,
Go Hamasaka
b  Institute for Molecular Science (IMS), Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan
,
Yasuhiro Uozumi
b  Institute for Molecular Science (IMS), Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan
,
Tsutomu Shinagawa
c  Osaka Municipal Technical Research Institute, 1-6-50 Morinomiya, Joto, Osaka, 536-8553, Japan
,
Osamu Shimomura
a  Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan   Email: atsushi.otaka@oit.ac.jp
,
Ryôki Nomura
a  Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Ohmiya, Asahi, Osaka 535-8585, Japan   Email: atsushi.otaka@oit.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 09 December 2015

Accepted after revision: 05 January 2016

Publication Date:
16 February 2016 (online)


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.

 
  • References and Notes

    • 1a Nanoparticles and Catalysis . Astruc D. Wiley-VCH; Weinheim: 2008
    • 1b Yasukawa T, Miyamura H, Kobayashi S. Chem. Soc. Rev. 2014; 43: 1450
    • 1c Yan N, Xiao C, Kou Y. Coord. Chem. Rev. 2010; 254: 1179
  • 2 Jeffery T. Tetrahedron Lett. 1994; 35: 3051
    • 3a Deraedt C, Astruc D. Acc. Chem. Res. 2014; 47: 494
    • 3b Fihri A, Bouhrara M, Nekoueishahraki B, Basset J.-M, Polshettiwar V. Chem. Soc. Rev. 2011; 40: 511
    • 4a Nasrollahzadeh M, Sajadi SM, Honarmand E, Maham M. New J. Chem. 2015; 39: 4745
    • 4b Wu L, Zhang X, Tao Z. Catal. Sci. Tech. 2012; 2: 707
    • 4c Bernechea M, de Jesus E, Lopez-Mardomingo C, Terreros P. Inorg. Chem. 2009; 48: 4491
    • 5a Srimani D, Sawoo S, Sarkar A. Org. Lett. 2007; 9: 3639
    • 5b Sreedhar B, Kumar S, Yada D. Synlett 2011; 1081
    • 5c Ranu BC, Dey R, Chattopadhyay K. Tetrahedron Lett. 2008; 49: 3430
    • 5d Nasrollahzadeh M, Sajadi SM, Honarmand E, Maham M. New J. Chem. 2015; 39: 4745
    • 5e Shah D, Kaur H. Curr. Catal. 2014; 3: 39
    • 5f Alacid E, Nájera C. Adv. Synth. Catal. 2006; 348: 945
    • 5g Paul A, , Chatterjee Rajkamal D, Banerjee S, Yadav S. RSC Adv. 2015; 5: 71253
    • 5h Kong F, Zhou C, Wang J, Yu Z, Wang R. ChemPlusChem 2013; 78: 536
    • 5i Ohtaka A, Sansano JM, Nájera C, Miguel-García I, Berenguer-Murcia Á, Cazorla-Amorós D. ChemCatChem 2015; 7: 1841
    • 6a Liao W.-T, Yang X.-J, Tseng Y.-Y, Wu C.-C, Liu L.-J, Tsai F.-Y. Asian J. Org. Chem. 2015; 4: 1112
    • 6b Liu X, Zhao X, Lu M. Catal. Lett. 2015; 145: 1549
    • 6c Nasrollahzadeh M, Banaei A. Tetrahedron Lett. 2015; 56: 500
    • 7a Chinchilla R, Nájera C. Chem. Soc. Rev. 2011; 40: 5084
    • 7b Gholinejad M, Hamed F, Biji P. Dalton Trans. 2015; 44: 14293
    • 7c Shunmughanathan M, Puthiaraj P, Pitchumani K. ChemCatChem 2015; 7: 666
    • 7d Nasrollahzadeh M, Mohammad Sajadi S, Maham M, Ehsani A. RSC Adv. 2015; 5: 2562
  • 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).
    • 9b Ohtaka A, Teratani T, Fujii R, Ikeshita K, Kawashima T, Tatsumi K, Shimomura O, Nomura R. J. Org. Chem. 2011; 76: 4052
  • 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.
    • 12a Albers PW, Möbus K, Wieland SD, Parker SF. Phys. Chem. Chem. Phys. 2015; 17: 5274
    • 12b Dressick WJ, Dulcey CS, Georger JH. Jr, Calabrese GS, Calvert JM. J. Electrochem. Soc. 1994; 141: 210
  • 13 No Ullmann coupling product was obtained in the absence of MeOH or on using PS-PdONPs as a catalyst.
  • 14 Zeng M, Du Y, Shao L, Qi C, Zhang X.-M. J. Org. Chem. 2010; 75: 2556