Tertiary-Amino-Functionalized Resin-Supported Palladium Catalyst for the Heterogeneous Suzuki–Miyaura Reaction of Aryl Chlorides
Received: 09 April 2015
Accepted after revision: 22 May 2015
09 July 2015 (online)
A palladium catalyst supported on a tertiary-amino-functionalized resin bearing N,N-dimethylamino substituents on the polystyrene-divinylbenzene-based resin was developed. The catalyst was effectively used for the ligand-free Suzuki–Miyaura reactions of less-reactive chloroarenes with arylboronic acids. No leached palladium species were detected in the reaction media after the reaction.
References and Notes
- 1 Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
- 2a McNamara CA, Dixon MJ, Bradley M. Chem. Rev. 2002; 3275
- 2b Phan NT. S, Sluys MV. D, Jones CW. Adv. Synth. Catal. 2006; 348: 609
- 2c Yin L, Liebscher J. Chem. Rev. 2007; 107: 133
- 2d Lamblin M, Nassar-Hardy L, Hierso J.-C, Fouquet E, Felpin F.-X. Adv. Synth. Catal. 2010; 352: 33
- 2e Climent MJ, Corma A, Iborra S. Chem. Rev. 2011; 111: 1072
- 2f Molnár A. Chem. Rev. 2011; 111: 2251
- 3a Sajiki H, Kurita T, Kozaki A, Zhang G, Kitamura Y, Maegawa T, Hirota K. J. Chem. Res. 2004; 593 ; Erratum: J. Chem. Res. 2005, 344
- 3b Sajiki H, Kurita T, Kozaki A, Zhang G, Kitamura Y, Maegawa T, Hirota K. Synthesis 2005; 537 ; Erratum: Synthesis 2005, 852
- 3c Maegawa T, Kitamura Y, Sako S, Udzu T, Sakurai A, Tanaka A, Kobayashi Y, Endo K, Bora U, Kurita T, Kozaki A, Monguchi Y, Sajiki H. Chem. Eur. J. 2007; 13: 5937
- 3d Kitamura Y, Sakurai A, Udzu T, Maegawa T, Monguchi Y, Sajiki H. Tetrahedron 2007; 63: 10596
- 3e Kitamura Y, Sako S, Udzu T, Tsutui A, Maegawa T, Monguchi Y, Sajiki H. Chem. Commun. 2007; 5069
- 3f Kitamura Y, Sako S, Tsutsui A, Monguchi Y, Maegawa T, Kitade Y, Sajiki H. Adv. Synth. Catal. 2010; 352: 718
- 3g Monguchi Y, Fujita Y, Endo K, Takao S, Yoshimura M, Takagi Y, Maegawa T, Sajiki H. Chem. Eur. J. 2009; 15: 834
- 3h Monguchi Y, Sakai K, Endo K, Fujita Y, Niimura M, Yoshimura M, Mizusaki T, Sawama Y, Sajiki H. ChemCatChem 2012; 4: 546
- 3i Hattori T, Tsubone A, Sawama Y, Monguchi Y, Sajiki H. Catalysts 2015; 5: 18
- 4a LeBlond CR, Andrews AT, Sun Y, Sowa JR. Jr. Org. Lett. 2001; 3: 1555
- 4b Tagata T, Nishida M. J. Org. Chem. 2003; 68: 9412
- 4c Arvela RK, Leadbeater NE. Org. Lett. 2005; 7: 2101
- 4d Ohtaka A, Sakaguchi E, Yamaguchi T, Hanasaka G, Uozumi Y, Shimomura O, Nomura R. ChemCatChem 2013; 5: 2167
- 4e Yuan B, Pan Y, Li Y, Yin B, Jiang H. Angew. Chem. Int. Ed. 2010; 49: 4054 ; Angew. Chem. 2010, 122, 4148
- 4f Kogan V, Aizenshtat Z, Popovitz-Biro R, Newmann R. Org. Lett. 2002; 4: 3529
- 4g Choudary BM, Madhi S, Chowdari NS, Kantam ML, Sreedhar B. J. Am. Chem. Soc. 2002; 124: 14127
- 4h Ciriminna R, Pandarus V, Gingras G, Béland F, Demma P, Pagliaro M. RSC Adv. 2012; 2: 10798
- 5a Li G, Yang H, Li W, Zhang G. Green Chem. 2011; 13: 2939
- 5b Karimi B, Akhavan PF. Inorg. Chem. 2011; 50: 6063
- 6a Wu L, Li B.-O, Huang Y.-Y, Zhou H.-F, He Y.-M, Fan Q.-H. Org. Lett. 2006; 8: 3605
- 6b Schweizer S, Becht J.-M, Drian CL. Org. Lett. 2007; 9: 3777
- 6c Sayah R, Glegola K, Framery E, Dufaud V. Adv. Synth. Catal. 2007; 349: 373
- 6d Pandarus V, Desplantier-Giscard D, Gingras G, Béland F, Ciriminna R, Pagliaro M. Org. Process Res. Dev. 2013; 17: 1492
- 6e Lee D.-H, Choi M, Yu B.-W, Ryoo R, Taher A, Hossain S, Jin M.-J. Adv. Synth. Catal. 2009; 351: 2912
- 6f Jin M.-J, Lee D.-H. Angew. Chem. Int. Ed. 2010; 49: 1119 ; Angew. Chem. 2010, 122, 1137
- 7a Das P, Sharma D, Shil AK, Kumari A. Tetrahedron Lett. 2011; 52: 1176
- 7b Yamada YM. A, Sarkar SM, Uozumi Y. J. Am. Chem. Soc. 2012; 134: 3190
- 8 Although a palladium catalyst embedded on commercial Amberlite IRA900 resin (an ammonium-bound polymer) was developed for the Suzuki–Miyaura reaction, aryl chlorides were hard to use as substrates (see ref. 7a).
- 9 See http://www.diaion.com/en/products/index.html.
- 10 Preparation of 7% Pd/WA30 (Scheme 1) A mixture of the lyophilized DIAION WA30 [3.00 g (net)] in a solution of Pd(OAc)2 [476 mg, 2.12 mmol (226 mg, palladium quantity)] in EtOAc (30 mL) was stirred under an Ar atmosphere at r.t. for 4 d. The resulting reddish solid was collected on a Kiriyama funnel (1 μm), washed with EtOAc (5 × 20 mL), H2O (5 × 20 mL), and MeOH (5 × 20 mL), and dried under vacuum for 12 h. The filtrate was concentrated in vacuo and then transferred to a 100 mL volumetric flask with H2O. Its atomic absorption analysis indicated that 1.78 ppm (178 μg) of palladium species were present. The collected solid was then stirred with NH2NH2·H2O (319 mg, 6.37 mmol) in H2O (30 mL) under Ar at r.t. for 1 d. The black solid was collected on a Kiriyama funnel (1 μm), washed with H2O (5 × 20 mL) and MeOH (5 × 20 mL), then dried under vacuum for 12 h to produce the Pd/WA30 (3.43 g). The filtrate was concentrated in vacuo and then transferred to a 100 mL volumetric flask with H2O. Its atomic absorption analysis indicated that 0.12 ppm (12 μg) of the palladium species were present. The palladium amount, which was not captured on WA30, was found to be 190 μg (178 + 12 μg), which means that the palladium ratio of Pd/WA30 was 6.6% [(226 – 0.19)/3430 × 100].
- 11 10% Pd/C- or 10% Pd/HP20-catalyzed reaction gave 4-phenylacetophenone as the product in 3% or 44% yield, respectively. 10% Pd/HP20 is more swellable in DMA compared to 7% Pd/WA30 (see Supporting Information), suggesting that absorption effect of 10% Pd/HP20 did not positively affect the reaction progress.
- 12 The Suzuki–Miyaura reaction between 4′-chloroacetophenone and phenylboronic acid using the 7% Pd/WA30, which was prepared without the reduction process by hydrazine, also proceeded, but it was slightly less effective. The desired 4-acetylbiphenyl was obtained in 97% yield after 6 h together with recovered 4′-chloroacetophenone in 1% yield.
- 13 Typical Procedure for the 7% Pd/WA30-Catalyzed Suzuki–Miyaura Reaction between Aryl Chlorides and Arylboronic Acids (Table 2 and Scheme 2) In the test tube were placed 7% Pd/WA30 (19.0 mg, 12.5 μmol), the aryl chloride (250 μmol), the arylboronic acid (375 μmol), Cs2CO3 (163 mg, 500 μmol), and DMA (1 mL). The mixture was stirred at 80 °C under an Ar atmosphere. The reaction progress was monitored by TLC analysis (hexane–EtOAc, 5:1). When the reaction was completed within 24 h, the mixture was cooled to r.t., diluted with Et2O (5 mL), and passed through a cotton filter. The catalyst on the filter was washed with Et2O (2 × 15 mL) and H2O (3 × 10 mL). The combined filtrate was separated into two layers. The aqueous layer was extracted with Et2O (20 mL), and the combined organic layers were washed with H2O (4 × 20 mL) and brine (20 mL), dried over Na2SO4, filtered, and concentrated in vacuo. To the residue was added CDCl3 (ca. 1 mL) and 1,4-dioxane (8.53 μL, 100 μmol). After the determination of the reaction yield by 1H NMR, the product was purified by silicagel column chlomatography using hexane–EtOAc (10:1) as eluents to give the corresponding biaryl. When the reaction was incomplete after 24 h, the reaction mixture was treated in the same manner as described above
- 14 The present cross-coupling reaction would be catalyzed by the palladium(0) species that is generated in situ under the reaction conditions, see: Choi M, Lee D.-H, Na K, Yu B.-W, Ryoo R. Angew. Chem. Int. Ed. 2009; 48: 3673 ; Angew. Chem. 2009, 121, 3727