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DOI: 10.1055/s-0029-1219816
Immobilization of Pd on Nanosilica Dendrimer as SILC: Highly Active and Sustainable Cluster Catalyst for Suzuki-Miyaura Reaction
Publication History
Publication Date:
16 April 2010 (online)
Abstract
Palladium acetate was noncovalently immobilized as a supported ionic liquid catalyst (SILC) in a nanosilica dendrimer, PAMDMAM, with the aid of an ionic liquid to form a cluster catalyst of palladium nanoparticles. The pseudo-homogeneous heterogenized catalyst, Pd-nanoPAMDMAM-SILC, was effective for Suzuki-Miyaura reactions of ortho-substituted aryl bromides or aryl triflates without a ligand in 50% aqueous ethanol in air at room temperature. The catalyst could be re-used up to five times in 93% average yield after simple centrifugation. TON reached 176,000.
Key words
dendrimers - heterogeneous catalysis - supported catalysis - palladium - cross-coupling
-
1a
Wight PA.Davis ME. Chem. Rev. 2002, 102: 3589 -
1b
Minakata S.Komatsu M. Chem. Rev. 2009, 109: 711 -
2a
Tsubokawa N.Ichioka H.Saitoh T.Fujiki K. React. Funct. Polym. 1998, 37: 75 -
2b
Murota M.Sato S.Tsubokawa N. Polym. Adv. Technol. 2002, 13: 144 -
2c
Wu XZ.Liu P.Pu QS.Sun QY.Su ZX. Talanta 2004, 62: 918 - Recent representative advances on SILC:
-
3a
Mehnert CP.Mozeleski EJ.Cook RA. Chem. Commun. 2002, 3010 -
3b
Riisager A.Wasserscheid P.van Hal R.Fehrmann R. J. Catal. 2003, 219: 452 -
3c
Huang J.Jiang T.Gao H.Han B.Liu Z.Wu W.Chang Y.Zhao G. Angew. Chem. Int. Ed. 2004, 43: 1397 -
3d
Breitenlechner S.Fleck M.Müller TE.Suppan A. J. Mol. Catal. A: Chem. 2004, 214: 175 -
3e
Riisager A.Fehrmann R.Flicker S.van Hal R.Hanmann M.Wasserscheid P. Angew. Chem. Int. Ed. 2005, 44: 815 -
3f
Mehnert CP. Chem. Eur. J. 2005, 11: 50 -
3g
Lou L.-L.Yu K.Ding F.Thou W.Peng X.Liu S. Tetrahedron Lett. 2006, 47: 6513 -
3h
Gua Y.Lia G. Adv. Synth. Catal. 2009, 351: 817 -
4a
Hagiwara H.Sugawara Y.Isobe K.Hoshi T.Suzuki T. Org. Lett. 2004, 6: 2325 -
4b
Hagiwara H.Sugawara Y.Hoshi T.Suzuki T. Chem. Commun. 2005, 2942 - 5
Hagiwara H.Ko KH.Hoshi T.Suzuki T. Chem. Commun. 2007, 2838 -
6a
Hagiwara H.Okunaka N.Hoshi T.Suzuki T. Synlett 2008, 1813 -
6b
Hagiwara H.Okunaka N.Hoshi T.Suzuki T. Synlett 2008, 1813 -
6c
Hagiwara H.Nakamura T.Okunaka N.Hoshi T.Suzuki T. Helv. Chim. Acta 2010, 93: 175 - 7
Hagiwara H.Sasaki H.Hoshi T.Suzuki T. Synlett 2009, 643 - For representative examples of dendrimer-encapsulated metal nanoparticle catalysts, see:
-
9a
Crooks RM.Zhao M.Sun L.Chechik V.Yeung LK. Acc. Chem. Res. 2001, 34: 181 -
9b
Mizugaki T.Murata M.Ooe M.Ebitani K.Kaneda K. Chem. Commun. 2002, 52 -
9c
Ooe M.Murata M.Mizugaki T.Ebitani K.Kaneda K. Nano Lett. 2002, 2: 999 -
9d
Ooe M.Murata M.Takahama A.Mizugaki T.Ebitani K.Kaneda K. Chem. Lett. 2003, 32: 692 -
9e
Scott RW.Datye A.Crooks RM. J. Am. Chem. Soc. 2003, 125: 3708 -
9f
Ooe M.Murata M.Mizugaki T.Ebitani K.Kaneda K. J. Am. Chem. Soc. 2004, 126: 1604 -
9g
Scott RWJ.Wilson OM.Crooks RM.
J. Phys. Chem. B 2005, 109: 692 -
9h
Astruc D.Lu F.Aranzaes JR. Angew. Chem. Int. Ed. 2005, 44: 7852 -
9i
Astruc D. Inorg. Chem. 2007, 46: 1884 - For recent reviews on Suzuki-Miyaura reaction, see:
-
10a
Miyaura N.Suzuki A. Chem. Rev. 1995, 95: 2457 -
10b
Littke AF.Fu GC. Angew. Chem. Int. Ed. 2002, 41: 4176 -
10c
Miyaura N. Top. Curr. Chem. 2002, 219: 11 -
10d
Hassan J.Sevignon M.Gozzi C.Schulz E.Lemaire M. Chem. Rev. 2002, 102: 1359 -
10e
Kotha S.Lahiri K.Kashinath D. Tetrahedron 2002, 58: 9633 -
10f
Bellina F.Carpita A.Rossi R. Synthesis 2004, 2419 -
10g
Alonso F.Beletskaya IP.Yus M. Tetrahedron 2008, 64: 3047 -
10h
Martin R.Buchwald SL. Acc. Chem. Res. 2008, 41: 1461 - 11
Rouhi AM. Chem. Eng. News 2004, 82: 49 - 12
Hoshi T.Saitoh I.Nakazawa T.Suzuki T.Sakai J.-I.Hagiwara H. J. Org. Chem. 2009, 74: 4013 ; and earlier references cited therein - Some selected Suzuki-Miyaura reactions in an aqueous alcohol:
-
13a
Marck G.Villiger A.Buchecker R. Tetrahedron Lett. 1994, 35: 3277 -
13b
Liu L.Zhang Y.Xin BJ. J. Org. Chem. 2006, 71: 3994 -
13c
Zhang G. Synthesis 2005, 537 -
13d
Arvela RK.Leadbeater NE.Collins MJ. Tetrahedron 2005, 61: 9349 -
13e
Chanthavong F.Leadbeater NE. Tetrahedron Lett. 2006, 47: 1909 -
13f
Hagiwara H.Ko KH.Hoshi T.Suzuki T. Synlett 2008, 618 - Immobilization of palladium on amorphous silica dendrimer was pioneered by Alper and co-workers by coordination on phosphonated-dendrimer silica surface:
-
14a
Reynhardt JPK.Alper H. J. Org. Chem. 2003, 68: 8353 -
14b
Antebi S.Arya P.Manzer LE.Alper H. J. Org. Chem. 2002, 67: 6623 -
14c
Chanthateyanonth R.Alper H. Adv. Synth. Catal. 2004, 346: 1375 -
14d
Touzani R.Alper H. J. Mol. Catal. A: Chem. 2005, 227: 197 -
14e
Lu S.-M.Alper H. J. Am. Chem. Soc. 2005, 127: 14776 -
14f
Zweni PP.Alper H. Adv. Synth. Catal. 2006, 348: 725 -
14g
Zweni PP.Alper H. Adv. Synth. Catal. 2004, 346: 849 -
14h
Alper H.Arya P.Bourque SC.Jefferson GR.Manzer LE. Can. J. Chem. 2000, 78: 920 -
14i
Chanthateyanonth R.Alper H.
J. Mol. Catal. A: Chem. 2003, 201: 23 -
14j
Reynhardt JPK.Yang Y.Sayari A.Alper H. Adv. Funct. Mater. 2005, 15: 1641 - For recent representative examples of ligandless Suzuki-Miyaura reaction catalyzed by heterogeneous catalyst on solid support, see:
-
15a
Kudo D.Masui Y.Onaka M. Chem. Lett. 2007, 36: 918 -
15b
Kazmaier U.Hähn S.Weiss TD.Kautenburger R.Maier WF. Synlett 2007, 2579 -
15c
Artok L.Bulut H. Tetrahedron Lett. 2004, 45: 3881 -
15d
Daku KML.Newton RF.Pearce SP.Vileb J.William JMJ. Tetrahedron Lett. 2003, 44: 5095
References and Notes
Hagiwara, H.; Kuroda, T.; Hoshi, T.; Suzuki, T. unpublished results.
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Preparation of
Pd-nanoPAMDMAM-SILC 5
NanoPAMDMAM 3 (200
mg) powder was added to a solution of [bmim]PF6 (19
mg, 10 wt%) and Pd(OAc)2
(36 mg, 0.16
mmol) in THF (2 mL) in open air. The homogeneous solution was stirred
at r.t. for 4 h, and evaporated to dryness under reduced pressure.
The resulting powder was rinsed with Et2O (2 mL) five
times. Each time, the ether solution was stirred for 10 min, centrifuged
for 10 min, and decanted to leave the powder. Evaporation of ether provided
Pd-nanoPAMDMAM-SILC 5 as a pale yellow powder
(247 mg, 0.5-0.6 mmol/g of Pd).
4-Phenylacetophenone (8a)
Potassium carbonate (138 mg,
1.0 mmol) and Pd-nanoPAMDMAM-SILC 5 (8
mg, 0.005 mmol) were added to a solution of 4-bromoacetophenone
(6a, 100 mg, 0.50 mmol) and phenylboronic
acid (7a, 85 mg, 0.70 mmol) in 50% aq
EtOH (2 mL) in open air. The solution was stirred at r.t. for 30
min, then centrifuged for 10 min. After decantation of the organic
layer, the powder was rinsed with Et2O-EtOH (1:1,
5 mL) five times. Each time, the resulting homogeneous solution
was centrifuged to precipitate the SILC. The combined organic layer
was evaporated to dryness under reduced pressure. Purification by
column chromatography (EtOAc-n-hexane = 1:10)
provided
4-phenylacetophenone (8a,
102 mg) quantitatively.
4-(2-Phenylphenyl)acetophenone (8c)
Potassium carbonate (138 mg,
1.0 mmol) and Pd-nanoPAMDMAM-SILC 5 (8
mg, 0.005 mmol) were added to a solution of 4-bromoacetophenone
(6a, 100 mg, 0.50 mmol) and (2-phenyl)phenylboronic
acid (7c, 85 mg, 0.70 mmol) in 50% aq
EtOH (2 mL) in open air. The solution was stirred at r.t. for 30
min, then centrifuged for 10 min. After decantation of the organic
layer, the powder was rinsed with Et2O-EtOH
(1:1, 5 mL) five times. Each time, the resulting homogeneous solution
was centrifuged to precipitate the SILC. The combined organic layer
was evaporated to dryness under reduced pressure. Purification by
column chromatography (EtOAc-n-hexane = 1:10)
provided 4-(2-phenylphenyl)acetophenone (8c,
134 mg) in 98% yield.
4-(4-Methoxyphenyl)acetophenone (8d) Potassium carbonate (138 mg, 1.0 mmol) and Pd-nanoPAMDMAM-SILC 5 (8 mg, 0.005 mmol) were added to a solution of 4-bromoacetophenone (6a, 101 mg, 0.50 mmol) and 4-methoxyphenylboronic acid (7d, 106 mg, 0.70 mmol) in 50% aq EtOH (2 mL) in open air. The solution was stirred at r.t. for 30 min, then centrifuged for 10 min. After decantation of the organic layer, the powder was rinsed with Et2O-EtOH (1:1, 5 mL) five times. Each time, the resulting homogeneous solution was centrifuged to precipitate the SILC. The combined organic layer was evaporated to dryness under reduced pressure. Purification by column chromatography (EtOAc-n-hexane = 1:3) provided 4-(4-methoxyphenyl)acetophenone (8d, 104 mg) in 90% yield.