Full Paper

Received: 7 September 2009 Revised: 29 December 2009 Accepted: 2 January 2010 Published online in Wiley Interscience: 2 March 2010

(www.interscience.com) DOI 10.1002/aoc.1624

Exploration of amino-functionalized ionic liquids as ligand and base for Heck reaction
Jie Liua , Hongqiang Liua and Lei Wanga,b
A kind of amino-functionalized ionic liquid has been prepared and investigated as ligand and base for the Heck reactions between aryl iodides and bromides with olens in the presence of a catalytic amount of Pd submicron powder in [Bmim]PF6 . The reactions generated the corresponding products in excellent yields under mild reaction conditions. The generality of this catalytic system to the different substrates also gave satisfactory results. The key feature of the reaction is that Pd species and ionic liquids were easily recovered and reused six times with constant activity. Copyright c 2010 John Wiley & Sons, Ltd. Keywords: Heck reaction; functionalized ionic liquids; Pd submicron powder

Introduction
Palladium-catalyzed coupling of olens with aryl and vinyl halides, known as the Heck reaction,[1,2] pioneered by Heck and Mizoroki,[3] is one of the most investigated transition-metal catalyzed carboncarbon bond formation reactions in organic synthesis.[4] Actually, the Heck reactions involving aryl iodides and bromides are catalyzed by almost any Pd(II) or Pd(0) catalyst precursor, usually at elevated temperatures.[5] In addition, Heck reactions are generally carried out in homogeneous systems in the presence of P-ligands, which are moisture- and air-sensitive and unrecoverable.[6] Because the Heck reaction products were found to be important intermediates in the preparation of materials,[7] natural products[8] and bioactive compounds,[9] this chemistry has been focused on discovering a new generation of catalyst systems, such as palladacycles and Pdcarbene complexes.[10,11] Nevertheless, several factors, such as the use of toxic, easily oxidable phosphines, and the utilization of harmful solvents such as DMF and volatile organic solvents, have hampered broad industrial application.[12] In the last decade, palladiumphosphine catalyzed Heck reactions in room temperature ionic liquids (RTILs) have gained increased attention in order to resolve one or more of these problems.[13 15] In view of the increasing demand for environmentally benign reaction processes, increased efforts have been put towards investigating the Heck reaction, including searching for phosphine-free methods, using a ligandfree palladium catalyst system and carrying out the Heck reaction in non-conventional reaction media such as water, ionic liquids or supercritical CO2 .[16 18] As an extension to our research in recyclable catalytic systems,[19] we were interested in the use of non-volatile RTILs as reaction media.[13,20] RTILs are liquids at or around room temperature, they are salts that do not normally need to be melted by means of an external heat source, and have a negligibly low vapor pressure (108 bar)[21] due to strong Coulombic interactions.[22] They are thus termed green solvents, in contrast to traditional volatile organic solvents, which makes them suitable for industrial applications.[23,24] Over the past decade, ionic liquids have gained increasing attention as promising reaction media or catalysts for synthetic chemistry.[13,25] It is known that an ionic liquid can act as a ligand or other function, except reaction media. Although RTILs are superior to conventional solvents in

many cases, only a very limited number of structures have been utilized. Most of the recent investigations have employed the use of 1,3-dialkylimidazolium salts.[26] It is desirable to develop a simpler and more concise synthetic procedure for the synthesis of functionalized ionic liquids (FILs), which act as reaction media and other functions in the carboncarbon bond formation reactions.[13] Herein, we wish to report the design and synthesis of the aminofunctionalized ionic liquids, which can act as reaction medium, ligand as well as base to the Pd-catalyzed Heck reaction on a recyclable basis. The general procedure for the preparation of amino-functionalized ionic liquids is shown in Scheme 1.

Experimental
Materials and Methods Melting points were recorded on a WRS-2B melting point apparatus and are uncorrected. IR spectra were obtained on a Nicolet Nexus 470 spectrophotometer. All 1 H NMR and 13 C NMR spectra were recorded on a 400 MHz Bruker FT-NMR spectrometer. TMS was used as an internal standard. Products were puried by ash chromatography on 230400 mesh silica gel. The chemicals and solvents were purchased from commercial suppliers (Aldrich, USA and Shanghai Chemical Company, China) and were used without purication prior to use. Preparation of Amino-functionalized IL 1[27] Under nitrogen atmosphere, 1-methylimidazole (8.21 g, 100 mmol) and 3-chloropropan-1-amine (9.36 g, 100 mmol) were

Correspondence to: Lei Wang, Huaibei Coal Teachers College, Chemistry, Huaibei, Anhui 235000, Peoples Republic of China. E-mail: leiwang@hbcnc.edu.cn

a Department of Chemistry, Huaibei Coal Teachers College, Huaibei, Anhui 235000, Peoples Republic of China b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, Peoples Republic of China

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Amino-functionalized ionic liquids as ligand and base for Heck reaction (5.0 ml), and ltered to remove the inorganic salt. The solvent was removed in vacuo to afford yellow viscous IL 3 (18.13 g, yield 87%).[29] 1 H NMR (400 MHz, D2 O): = 8.78 (s, 1 H), 7.52 (s, 1 H), 7.44 (s, 1 H), 4.29 (t, J = 7.5 Hz, 2 H), 3.84 (s, 3 H), 3.02 (m, 2 H), 2.22 (m, 2 H); 13 C NMR (100 MHz, D2 O): = 27.42, 36.10, 36.49, 46.45, 122.13, 122.89, 136.18; IR (KBr): 3432, 3147, 2980, 2973, 2634, 1594, 1576, 1521, 1507, 1463, 1172, 848, 757, 622 cm1 . The 1 H and 13 C spectra were found to be in agreement with Wu et al.[29] General Procedure for Heck Reaction Catalyzed by Aminofunctionalized IL 3 and Pd Submicron Powder Under nitrogen atmosphere, an oil bath with a round-bottomed ask containing 4-iodoanisole (234 mg, 1.0 mmol), n-butyl acrylate (128 mg, 1.0 mmol), Pd submicron powder (1.0 mg, 0.01 mmol) and amino-functionalized IL 3 (285 mg, 1.0 mmol) in [Bmim]PF6 (2.0 ml) was heated to 120 C during a period of 24 h. After cooling to room temperature, the product was extracted from the mixture with EtOAc (5.0 ml 3). The combined organic layers were washed with H2 O and brine, dried over MgSO4 , and the solvent evaporated under reduced pressure. Typically, purication by chromatography of the crude mixture was performed to give the desired pure product in 93% yield (234 mg). (E)-Stilbene White solid; m.p. 122123 C (lit.[30] 120122 C). IR (KBr): 3022, 1586, 1494, 1457, 1366, 967, 760, 693 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 7.357.50 (m, 4 H), 7.317.33 (m, 4 H), 7.23 (t, J = 7.5 Hz, 2 H), 7.09 (s, 2 H). 13 C NMR (100 MHz, CDCl3 ): = 137.3, 128.6, 128.4, 127.6, 126,5. The 1 H and 13 C spectra were found to be in agreement with Cui et al.[31] (E)-4-Methoxystilbene Light yellow solid; m.p. 136138 C (lit.[32] 135137 C). IR (KBr): 2961, 1604, 1512, 1446, 1293, 1025, 965, 862, 753, 686 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 3.73 (s, 3H), 6.90 (d, J = 8.7 Hz, 2 H), 6.906.96 (m, 2 H), 7.00 (d, J = 15.9 Hz, 1 H), 7.23 (t, J = 7.5 Hz, 2 H), 7.357.41 (m, 4 H). 13 C NMR (100 MHz, CDCl3 ): = 159.3, 137.6, 130.1, 128.6, 128.2, 127.7, 127.2, 126.6, 126.2, 114.1, 55.3. The 1 H and 13 C spectra were found to be in agreement with Cui et al.[31] (E)-4-Methylstilbene Light yellow solid; m.p. 121122 C (lit.[30] 119120 C). IR (KBr): 3022, 2914, 2848, 1606, 1444, 967, 810, 743, 698 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 2.45 (s, 3 H), 7.157.29 (m, 4 H), 7.357.42 (m, 3 H), 7.52 (d, J = 7.9 Hz, 2 H). 13 C NMR (100 MHz, CDCl3 ): = 137.5, 134.5, 129.4, 128.6, 127.6, 127.3, 126.4, 126.3, 21.2. The 1 H and 13 C spectra were found to be in agreement with Cui et al.[31] (E)-4-Cyanostilbene White solid; m.p. 117119 C (lit.[33] 117.4117.7 C). IR (KBr): 3024, 2918, 2225, 1601, 973, 826, 759 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 7.05 (d, J = 15.8 Hz, 1 H), 7.317.39 (m, 3 H), 7.517.60 (m, 6 H). 13 C NMR (100 MHz, CDCl3 ): = 141.8, 136.2, 132.3, 132.2, 128.7, 128.5, 127.0, 126.8, 126.6, 118.9, 110.4. The 1H and 13 C spectra were found to be in agreement Cui et al.[31]

N + Cl

NH2

Reflux, 24h EtOH, N2

N Cl-

NH2 IL 1

IL 1

KOH NaBF4, r.t. 48 h KOH KPF6, r.t. 48 h

N BF4N PF6-

NH2

IL 2

IL 1

NH2

IL 3

R1

Pd Powder IL 1, 2 or 3 + R2 [Bmim]PF6 N N PF6-

R2 R1

[Bmim]PF6 =

Scheme 1. Synthesis of amino-functionalized ionic liquids and their applications in Heck reaction.

dissolved in 50 ml of dry ethanol under stirring. The resulting mixture was reuxed for 24 h under nitrogen protection. After removal of ethanol in vacuum, the solid residue was dissolved in water. Then the pH value of the solution was adjusted to 10 by the addition of potassium hydroxide. The obtained solution was concentrated under vacuum and then extracted with ethanoltetrahydrofuran (v/v, 1 : 1, 75.0 ml 2). The combined extracts were concentrated to give the product IL 1 as a pale yellow viscous liquid (13.08 g, yield 73%).[27] 1 H NMR (400 MHz, D2 O): = 8.80 (s, 1 H), 7.54 (s, 1 H), 7.48 (s, 1 H), 4.34 (t, J = 7.4 Hz, 2 H), 3.90 (s, 3 H), 3.08 (m, 2 H), 2.28 (m, 2 H); 13 C NMR (100 MHz, D2 O): = 27.41, 35.89, 36.43, 46.44, 122.15, 123.97, 136.19; IR (KBr): 3157, 2963, 2753, 1634, 1579 cm1 . The 1 H and 13 C spectra were found to be in agreement with the Fu and Liu.[27] Preparation of Amino-functionalized IL 2[28] IL 1 (13.08 g, 73.0 mmol) subsequently through ion exchange with sodium tetrauoroborate (8.72 g, 80.0 mmol) in ethanolwater (v/v, 1 : 1, 15.0 ml) was performed for 48 h at room temperature. The suspension was ltered to remove the precipitated bromide salt and the organic phase was concentrated. The residue was then re-dissolved in small amount of chloroform (5.0 ml), and ltered to remove the inorganic salt. The solvent was removed in vacuo to afford yellow viscous IL 2 (15.11 g, yield 91%).[28] 1 H NMR (400 MHz, D2 O): = 8.75 (s, 1 H), 7.58 (s, 1 H), 7.50 (s, 1 H), 4.38 (t, J = 8.2 Hz, 2 H), 3.92 (s, 3 H), 3.14 (m, 2 H), 2.35 (m, 3 H); 13 C NMR (100 MHz, D O): = 27.40, 35.87, 35.90, 46.39, 122.09, 2 123.88, 136.26; IR (KBr): 3426, 3143, 2955, 2739, 2643, 2504, 2015, 1574, 1506, 1457, 1339, 1285, 1232, 1169, 1085, 1021, 831, 756, 621 cm1 . The 1 H and 13 C spectra were found to be in agreement with Tan et al.[28] Preparation of Amino-functionalized IL 3[29] IL 1 (13.08 g, 73.0 mmol) subsequently through ion exchange with potassium hexauorophosphate (14.72 g, 80.0 mmol) in ethanolwater (v/v, 1 : 1, 15.0 ml) was performed for 48 h at room temperature. The suspension was ltered to remove the precipitated bromide salt and the organic phase was concentrated. The residue was then re-dissolved in small amount of chloroform

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J. Liu, H. Liu and L. Wang (E)-4-(Triuoromethyl)stilbene Light yellow solid; m.p. 132134 C (lit.[34] 132134 C). IR (KBr): 3025, 2846, 1626, 1554, 1418, 1326, 1167, 1111, 1070, 973, 827 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 7.58 (m, 4 H), 7.52 (d, J = 7.2 Hz, 2 H), 7.39 (m, 2 H), 7.29 (m, 1 H), 7.18 (d, J = 16.2 Hz, 1 H), 7.09 (d, J = 16.5 Hz, 1 H).13 C NMR (100 MHz, CDCl3 ): = 140.6, 136.2, 132.1, 132.0, 131.3, 128.6, 128.1, 127.2, 126.7, 126.6, 125.6, 125.45. The 1 H and 13 C spectra were found to be in agreement with Warner and Sutherland.[35] (E)-3-(Triuoromethyl)stilbene Light yellow solid; m.p. 6567 C (lit.[36] 6667 C). IR (KBr): 3039, 2854, 1619, 1558, 1497, 1452, 1342, 1169, 1116, 962, 805, 696 cm1 . 1 H NMR (400 MHz, CDCl ): = 7.75 (s, 1 H), 7.68 (m, 1 H), 7.557.47 3 (m, 4 H), 7.427.34 (m, 2 H), 7.27 (m, 1 H), 7.16 (d, J = 16.3 Hz, 1 H), 7.12 (d, J = 16.3 Hz, 1 H). 13 C NMR (100 MHz, CDCl3 ): = 138.4, 136.9, 131.2, 130.8, 129.6, 129.1, 128.9, 128.4, 127.2, 126.8, 124.3, 124.2, 123.1. The 1 H and 13 C spectra were found to be in agreement with Cui et al.[31] (E)-2-(Triuoromethyl)stilbene Light yellow liquid.[37] IR (lm): 3030, 2850, 1621, 1550, 1428, 1341, 1162, 1113, 965, 815, 695 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 7.707.09 (m, 11 H). 13 C NMR (100 MHz, CDCl3 ): = 137.2, 136.5, 132.7, 131.8, 131.7, 129.5, 128.7, 128.4, 127.5, 127.3, 127.1, 126.2, 124.5. The 1 H and 13 C spectra were found to be in agreement with Wang and Wnuk.[37] (E)-2-Methylstilbene Light yellow solid; m.p. 3132 C (lit.[38] 3032 C). IR (KBr): 2923, 1604, 1492, 1454, 967, 763 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 7.567.49 (m, 3 H), 7.367.13 (m, 6 H), 7.07 (d, J = 16.2 Hz, 2 H), 2.38 (s, 3 H). 13 C NMR (100 MHz, CDCl3 ): = 137.6, 136.2, 135.8, 130.4, 130.0, 128.7, 127.6, 127.6, 126.5, 126.2, 125.4, 20.2. The 1 H and 13 C spectra were found to be in agreement with Lindhardt et al.[39] n-Butyl (E)-3-(4-methoxyphenyl)prop-2-enoate Light yellow liquid.[31] IR (lm): 2956, 2930, 1603, 1462, 982, 826 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 0.94 (t, J = 7.8 Hz, 3 H), 1.401.46 (m, 2 H), 1.641.71 (m, 2 H), 3.80 (s, 3 H), 4.19 (t, J = 6.9 Hz, 2 H), 6.31 (d, J = 15.4 Hz, 1 H), 6.88 (d, J = 8.2 Hz, 2 H), 7.45 (d, J = 8.2 Hz, 2 H), 7.63 (d, J = 15.8 Hz, 1 H).13 C NMR (100 MHz, CDCl3 ): = 167.2, 161.9, 144.0, 129.5, 127.2, 115.6, 114.2, 64.1, 55.2, 30.7, 19.1, 13.6. The 1 H and 13 C spectra were found to be in agreement with Cui et al.[31] n-Butyl (E)-cinnamate IR (lm): 3065, 2958, 1708, 1631, 1462, 1326, NMR (400 MHz, CDCl3 ): = 0.98 (t, J = 7.3 Hz, 766, 3 H), 1.421.56 (m, 2 H), 1.701.72 (m, 2 H), 4.21 (t, J = 6.7 Hz, 2 H), 6.47 (d, J = 16.0 Hz, 1 H), 7.357.38 (m, 3 H), 7.517.53 (m, 2 H), 7.65 (d, J = 16.0 Hz, 1 H). 13 C NMR (100 MHz, CDCl3 ): = 167.2, 144.4, 134.6, 130.1, 128.7, 128.1, 118.2, 64.3, 30.7, 19.1, 13.6. The 1 H and 13 C spectra were found to be in agreement with Cui et al.[31] 688 cm1 . 1 H Light yellow liquid.[31] Ethyl (E)-3-(2-triuoromethylphenyl)prop-2-enoate Light yellow liquid.[42] IR (lm): 3083, 2985, 1723, 1635, 1489, 1389, 1317, 1165, 1125,1037, 980, 766, 652 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 8.08 (d, J = 15.8 Hz, 1 H), 7.757.46 (m, 4 H), 6.42 (d, J = 15.8 Hz, 1 H), 4.28 (q, J = 7.1 Hz, 2 H), 1.34 (t, J = 6.0 Hz, 3 H).13 C NMR (100 MHz, CDCl3 ): = 166.8, 142.3, 132.5, 131.6, 128.2, 126.6, 125.3, 122.4, 61.6, 14.2. The 1 H were found to be in agreement with Chatterjee et al.[42] Ethyl (E)-3-(4-triuoromethylphenyl)prop-2-enoate Light yellow solid; m.p. 3133 C (lit.[43] 3132 C). IR (KBr): 3076, 2984, 1712, 1643, 1417, 1325, 1284, 1170, 1069, 985, 833 cm1 . 1 H NMR (400 MHz, CDCl ): = 7.68 (d, J = 15.9 Hz, 1 H), 7.61(m, 3 4 H), 6.50 (d, J = 15.9 Hz, 1 H), 4.29 (q, J = 7.2 Hz, 2 H), 1.35 (t, J = 7.0 Hz, 3 H). 13 C NMR (100 MHz, CDCl3 ): = 166.2, 142.7, 137.6, 132.1, 129.5, 128.2, 125.5, 120.7, 60.6, 14.4. The 1 H and 13 C spectra were found to be in agreement with Chen et al.[44] n-Butyl (E)-3-(4-cyanophenyl) prop-2-enoate Light yellow liquid.[32] IR (lm): 2959, 2886, 2221, 1715, 1641, 1606, 1411, 987, 836 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 0.97 (t, J = 7.6 Hz, 3 H), 1.341.48 (m, 2 H), 1.591.64 (m, 2 H), 4.21 (t, J = 6.8 Hz, 2 H), 6.50 (d, J = 15.7 Hz, 1 H), 7.617.73 (m, 5 H). 13 C NMR (100 MHz, CDCl3 ): = 166.2, 142.1, 138.6, 132.3, 128.0, 121.0, 117.9, 113.3, 64.5, 30.5, 19.3, 13.8. The 1 H and 13 C spectra were found to be in agreement with Cui et al.[31] n-Butyl (E)-3-(4-methylphenyl)prop-2-enoate Light yellow liquid.[31] IR (lm): 3012, 2956, 1719, 1604, 1517, 984, 810 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 0.86 (t, J = 7.4 Hz, 3 H), 1.291.38 (m, 2 H), 1.551.62 (m, 2 H), 2.25 (s, 3 H), 4.10 (t, J = 6.7 Hz, 2 H), 6.31 (d, J = 16.0 Hz, 1 H), 7.06 (d, J = 8.0 Hz, 2 H), 7.30 (d, J = 8.0 Hz, 2 H), 7.58 (d, J = 16.0 Hz, 1 H). 13 C NMR (100 MHz, CDCl3 ): = 167.1, 144.4, 140.4, 131.63, 129.5, 127.9, 117.0, 64.2, 30.7, 21.3, 19.1, 13.6. The 1 H and 13 C spectra were found to be in agreement with Cui et al.[31] Ethyl (E)-3-(3-nitrophenyl)prop-2-enoate Light yellow solid; m.p. 7475 C (lit.[40] 74.374.6 C). IR (KBr): 3073, 2983, 1717, 1645, 1525, 1483, 1353, 1328, 1187, 997, 871, 747, 666 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 8.53 (t, J = 1.7 Hz, 1 H), 8.21(dd, J = 8.4, 1.6 Hz, 1 H), 8.17 (d, J = 8.0 Hz, 1 H), 7.76 (d, J = 16.4 Hz, 1 H), 7.71 (t, J = 8.0 Hz, 1 H), 6.84 (d, J = 16.0 Hz, 1 H), 4.21 (q, J = 7.2 Hz, 2 H), 1.26 (t, J = 7.0 Hz, 3 H). 13 C NMR (100 MHz, CDCl3 ): = 166.8, 149.2, 142.6, 136.4, 134.0, 130.2, 124.4, 122.8, 121.4, 59.6, 14.6. The 1 H and 13 C spectra were found to be in agreement with Bouziane et al.[41] n-Butyl (E)-3-(4-nitrophenyl)prop-2-enoate Light yellow solid; m.p. 6365 C (lit.[32] 6465 C). IR (KBr): 3058, 2958, 1709, 1601, 1493, 1308, 982, 759 cm1 . 1 H NMR (400 MHz, CDCl3 ): = 0.97 (t, J = 7.4 Hz, 3 H), 1.401.50 (m, 2 H), 1.671.74 (m, 2 H), 4.24 (t, J = 6.5 Hz, 2 H), 6.56 (d, J = 15.8 Hz, 1 H), 7.697.73 (m, 3 H); 8.238.25 (m, 2 H). 13 C NMR (100 MHz, CDCl3 ): = 165.7, 148.2, 141.2, 140.3, 128.4, 123.8, 122.3, 64.5, 30.4, 18.9, 13.4. The 1 H and 13 C spectra were found to be in agreement with Cui et al.[31]

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Amino-functionalized ionic liquids as ligand and base for Heck reaction

Results and Discussion

The synthesis of amino-functionalized IL 1, 2 and 3 is illustrated in Scheme 1. They were readily prepared through a straightforward two-step procedure from commercially available starting materials and reagents in good yields. The N-methyl imidazole was reacted with 3-chloropropan-1-amine with 1 : 1 molar ratio in ethanol under reux temperature for 24 h to afford IL 1 in 73% yield. This chloride salt (IL 1) then reacted with sodium tetrauoroborate or potassium hexauorophosphate at room temperature in ethanolwater for 48 h to obtain the corresponding amino-functionalized ionic liquids containing tetrauoroborate or hexauorophosphate anions, IL 2 and 3, respectively. The ionic liquids were further puried by drying in a vacuum to remove the residual starting materials, reagents or organic solvents. In order to evaluate the catalytic activity of Pd-catalyzed Heck reaction in the presence of IL 1, 2 and 3, initially, we focused our attention on the reaction of 4-iodoanisole with n-butyl acrylate under the reaction conditions involving 4-iodoanisole (1.0 mmol), n-butyl acrylate (1.0 mmol), Pd submicron powder (0.01 mmol), IL 1, 2 or 3 (1.0 mmol), at 120 C in [Bmim]Cl, [Bmim]BF4 or [Bmim]PF6 (2.0 ml), respectively. It was found that IL 3 in [Bmim]PF6 exhibits a high activity to palladium-catalyzed Heck reaction, while the corresponding BF4 and Br ionic liquids, IL 2 with [Bmim]BF4 and IL 1 with [Bmim]Cl, demonstrated the lower catalytic activity (Table 1, entries 1, 3, 5, 7 and 8). The inuence of anions in functionalized ionic liquids on the catalytic activity of palladiumcatalyzed Heck reaction is Br < BF4 < PF6 . For comparison, the experimental results also revealed that, in the absence of amino-functionalized ionic liquids, 1, 2 and 3, Pd submicron powder clearly showed no catalytic activity to the Heck reaction (Table 1, entries 2, 4 and 6). When the reaction was carried out in [Bmim]BF4 with additional of K2 CO3 (2.0 mmol) added to the reaction system, only a trace amount of the desired Heck coupling product was isolated (Table 1, entry 9). This is presumably due to the effective N-ligand of IL 1, 2 and 3, in the palladium powder catalyzed reaction.[13] Encouraged by this result, we continued our research to further optimization of the reaction conditions. We then turned our attention to investigating the effects of palladium source on the Heck reaction. Pd submicron powder was screened as the optimal one in the presence of 1.0 mol% amount at 120 C, whereas other palladium sources such as PdCl2 , Pd(Cl)2 (PPh3 )2 and Pd(PPh3 )4 were substantially less effective (Table 2). Although Pd(OAc)2 also achieved satisfactory yield (92%), palladium submicron powder was superior to Pd(OAc)2 in the recovery and reuse procedure for the further consideration. After exploring a wide array of reaction conditions at the outset of our studies, we were pleased to nd that the treatment of 4-iodoanisole and n-butyl acrylate in the presence of 1.0 mol% Pd submicron powder and using amino-functionalized IL 3 (1.0 equiv.) in [Bmim]PF6 at 120 C for 24 h generated the expected product in excellent yield (93%, Table 1, entry 4 and Table 2, entry 1). To investigate the scope of the present method, the Heck alkenation of n-butyl acrylate and ethyl acrylate with a variety of iodoarenes and bromoarenes, containing electron-withdrawing or electron-donating substituents, was investigated. The results in Table 3 indicated that the conversions, regioselectivities (>99% trans products) and yields were satisfactory under optimized reaction conditions (Table 3, entries 112). In addition, to determine the scope of this catalytic system, other olens

Table 1. Effect of the amino-functionalized ionic liquids on the Heck reactiona

I + H3CO CO2Bu-n Pd powder (Submicron) CO2Bu-n H3CO

Entry 1 2 3 4 5 6 7 8 9

Amino-functionalized IL IL 1 IL 2 IL 3 IL 1 IL 2

Common IL [Bmim]Cl [Bmim]Cl [Bmim]BF4 [Bmim]BF4 [Bmim]PF6 [Bmim]PF6 [Bmim]PF6 [Bmim]PF6 [Bmim]BF4

Yieldb (%) 31 0 76 trace 93 trace 58 85 tracec

a 4-Iodoanisole (234 mg, 1.0 mmol), n-butyl acrylate (128 mg, 1.0 mmol), Pd submicron powder (1.0 mg, 0.01 mmol), aminofunctionalized IL (1.0 mmol) and in common IL (2.0 ml) at 120 C for 24 h. b Isolated yield. c In the presence of K CO (2.0 mmol). 2 3

Table 2. Effect of palladium source on the Heck reactiona

I + H3CO Pd Source IL 3 CO2Bu-n H3CO

CO2Bu-n

Entry 1 2 3 4 5

Palladium source Pd submicron powder Pd(OAc)2 PdCl2 Pd(Cl)2 (PPh3 )2 Pd(PPh3 )4

Yieldb (%) 93 92 51 60 34

a 4-Iodoanisole (234 mg, 1.0 mmol), n-butyl acrylate (128 mg, 1.0 mmol), Pd source (0.01 mmol) and IL 3 (285 mg, 1.0 mmol) in [Bmim]PF6 (2.0 ml) at 120 C for 24 h. b Isolated yields.

substrates, such as styrene, were also examined, and good results were also obtained under the identical reaction conditions (Table 3, entries 1324). It should be noted that the alkenation of haloarenes was tolerant of ortho- and meta-substitution of the aryl iodide and afforded the desired products in excellent yields (Table 3, entries 4, 7 and 1820). However, when aryl chlorides served as organic halide substrates, poor yields of the corresponding products were obtained under the same reaction conditions, owing to the much lower reactivity of their carbonchlorine bond.[13,45,46] In addition, the result of the olenation reaction of iodobenzene with internal olens, such as ethyl cinnamate, was found to be negative (Table 3, entry 25). To screen the recyclability of this catalytic system, after carrying out a reaction, isolating the product from the reaction mixture, washing with solvents, drying and recovering aminofunctionalized IL 3, Pd species and [Bmim][PF6 ], fresh starting materials were charged into the reaction system. The reactions

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J. Liu, H. Liu and L. Wang amount of Pd submicron powder in [Bmim]PF6 under base-free and phosphine-free reaction conditions. The reactions generated the corresponding products in excellent yields under mild reaction conditions. It should be pointed out that Pd species and ionic liquids can be easily recycled and reused with the same efcacies for six cycles. Currently, further efforts to extend the application of the system in other palladium-catalyzed transformations are underway in our laboratory. Acknowledgments We gratefully acknowledge nancial support by the National Natural Science Foundation of China (no. 20772043), and the Key Project of Science and Technology of the Department of Education, Anhui Province, China (no. ZD2007005-1).

Table 3. Heck reactions catalyzed by Pd submicron powder and amino-functionalized IL 3a Entry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Olen H2 C CHCO2 C4 H9 -n H2 C CHCO2 C4 H9 -n H2 C CHCO2 C4 H9 -n H2 C CHCO2 C2 H5 H2 C CHCO2 C4 H9 -n H2 C CHCO2 C4 H9 -n H2 C CHCO2 C2 H5 H2 C CHCO2 C2 H5 H2 C CHCO2 C4 H9 -n H2 C CHCO2 C4 H9 -n H2 C CHCO2 C4 H9 -n H2 C CHCO2 C4 H9 -n C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CH2 C6 H5 CH CHCO2 C2 H5 Aryl halide p-CH3 OC6 H4 I C6 H5 I p-CH3 C6 H4 I m-NO2 C6 H4 I p-NO2 C6 H4 I p-CNC6 H4 I o-CF3 C6 H4 I p-CF3 C6 H4 I p-CH3 OC6 H4 Br p-CH3 C6 H4 Br p-NO2 C6 H4 Br p-CNC6 H4 Br C6 H5 I p-CH3 OC6 H4 I p-CH3 C6 H4 I p-CNC6 H4 I p-CF3 C6 H4 I m-CF3 C6 H4 I o-CF3 C6 H4 I o-CH3 C6 H4 I p-CH3 OC6 H4 Br p-CH3 C6 H4 Br p-CNC6 H4 Br C6 H5 Br C6 H5 I Yieldb (%) 93 92 90 78 92 91 89 90 83 82 89 87 84 82 85 92 85 89 88 87 73 80 89 86 0

References
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a Alkene (1.0 mmol), aryl halide (1.0 mmol), Pd submicron powder (1.0 mg, 0.01 mmol), IL 3 (285 mg, 1.0 mmol) in [Bmim]PF6 (2.0 ml) at 120 C for 24 h. b Isolated yield.

Table 4. Successive trials by using recoverable Pd submicron powder and IL 3a

I + H3CO Recycle Pd IL 3 H3CO CO2Bu-n

CO2Bu-n

Trial 1 2 3

Yieldb (%) 93 93 92

Trial 4 5 6

Yieldb (%) 92 92 90

a 4-Iodoanisole (234 mg, 1.0 mmol), n-butyl acrylate (128 mg, 1.0 mmol), Pd submicron powder (1.0 mg, 0.01 mmol), IL 3 (285 mg, 1.0 mmol) in [Bmim]PF6 (2.0 ml) at 120 C for 24 h. b Isolated yield.

still proceeded well. Pd, IL 3 and [Bmim]PF6 were recycled six times without decreases in product yields.

Conclusion
In conclusion, we have developed a kind of amino-functionalized ionic liquids as ligand and base for the Heck reactions between aryl iodides and bromides with olens in the presence of a catalytic

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Amino-functionalized ionic liquids as ligand and base for Heck reaction

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