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1 Electronic Supplementary Material (ESI) for Catalysis Science & Technology. This journal is The Royal Society of Chemistry 205 Supporting Information Novel glycosyl nanoparticles: efficient and recoverable catalysts for C-C cross-couplings Hong-yun Shen, a Chao Shen,* b Chao Chen, c An-ming Wang a and Peng-fei Zhang* a a College of Material,Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 30036, China b College of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou 3005, China c College of Life sciences, Huzhou Teachers College, Huzhou, 33000, China. General Information Experimental Section Characterization of the Products: Copies of NMR and GC-MS Spectra X-ray Crystal Data for GPT-Pd catalyst 5c References...63

2 . General Information The starting materials were commercially available and were used without further purification except solvents. The products were isolated by column chromatography on silica gel ( mesh) using petroleum ether (60-90 o C) and ethyl acetate. Melting points were determined on an X-5 Data microscopic melting point apparatus. and 3 C NMR spectra were recorded on a Bruker Advance 400 spectrometer at ambient temperature with CDCl3 or DMSO-d6 as solvent unless otherwise noted and tetramethylsilane (TMS) as the internal standard. Mass spectra (EI-MS) were acquired on an Agilent 5975 spectrometer. Mass spectra (GC-MS) were acquired on an Agilent 5975 spectrometer. Transmission electron microscopy (TEM) images were taken on FEI T20 microscope. ICP-AES metal determinations were carried out on a Perkin-Elmer Optima 300 XL inductively coupled plasma atomic emission spectrometer equipped with an axial torch, segmented array charge-coupled device detector, and Babington-type nebulizer with cyclonic spray chamber for sample introduction. The small-angle X-ray diffraction (SAXRD) data were taken on a German Bruker D4 X-ray diffractometer with Niltered Cu Ka radiation (40 kv, 40 ma). Thermogravimetric analyses were performed with a SII Nano Technology EXTAR TG/DTA7220 thermal analyzer at 0 C/min in nitrogen atmosphere (0 ml/min). 5 mg of each sample in an alumina pan was analyzed in the C temperature range. Analytical thin layer chromatography (TLC) was performed on Merk precoated TLC (silica gel 60 F254) plates. The sugar substrates were prepared according to our previous reports. All compounds were characterized by H NMR and mass spectroscopy, which are consistent with those reported in the literature. 2-5 The quinolone bromides was prepared according to a similar reference Experimental Section General Procedure for synthesis of glycosyl pyridyl-triazole@palladium nanoparticle catalysts 5a-e Synthesis of GPT-Pd catalyst 5c: PdX2(X = OAc, Cl, Br) ( 0.50 mmol) was dissolved in anhydrous toluene (20.0 ml) and 4a-c (0.60 mmol) was added. The solid-liquid mixture was stirred for 6 h at room temperature, during this course, the yellow precipitate slowly appeared and after which the solid was filtered, washed thoroughly with large volume of 2

3 acetone in order to remove any adsorbed palladium and finally dried at 30 o C under vacuum. The nanoparticle catalysts was obtained as light yellow powder. General procedure for Suzuki-Miyaura coupling reaction between aryl halides and arylboronic acids. The Suzuki reaction was performed in a 0 ml round- bottomed flask, aryl halide (.0 mmol), arylboronic acid (.5 mmol), GPT-Pd catalysts 5 (0.025 mol% respect to aryl halides), K2CO3 (.5 mmol) and water (3 ml) were charged and stirred at 80 to00 o C under air. The reaction progress was monitored by TLC. After completion of the reaction, the mixture was allowed to cool to room temperature. Then the aqueous phase was extracted with CH2Cl2 for 3 times (3 2 ml). Then the combined organic layers were dried over anhydrous Na2SO4, concentrated under vacuum and purified by column chromatography (n-hexane/ethyl acetate 0:) to afford the desired product. General procedure for Heck reaction between aryl halides and olefins. The Heck reaction was performed in a 0 ml round- bottomed flask, aryl halide (0.5 mmol), olefins (0.6 mmol), GPT-Pd catalysts 5 (0.025 mol% respect to aryl halides), Et3N (.5 mmol) and a mixture of water and DMSO (:, 3 ml) were charged and stirred at 80 to00 o C under air. Monitoring of the reaction, workup procedure, and purification of the Heck-coupled products were performed as described for the Suzuki-Miyaura coupling reactions. General procedure for Sonogashira coupling reaction between aryl halides and terminal alkynes. The Sonogashira coupling reaction was performed in a 0 ml round- bottomed flask, aryl halide (.0 mmol), terminal alkynes (.5 mmol), GPT-Pd catalysts 5 (0.025 mol% respect to aryl halides), Et3N (.5 mmol) and a mixture of water and DMSO (:, 3 ml) were charged and stirred at 80 to00 o C under air. Monitoring of the reaction, workup procedure, and purification of the Sonogashira-coupled products were performed as described for the Suzuki-Miyaura coupling reactions. 3

4 General procedure for the catalyst recycling experiment. 4-iodoanisole 6a ( mmol), phenylboronic acid 7a (.5 mmol), GPT-Pd catalyst 5c (0.025 mol%), K2CO3 (.5 mmol) and in water (3 ml) was added to 3 ml water and ether was heated under air in an oil bath at 80 o C. After the completion of the reaction, the product was separated using ethyl acetate extraction and the catalyst by centrifugation (5000 rpm, 5 min). The products were purified by column chromatography. The catalyst was washed with ethyl acetate twice and was dried for 2 h at 50 C. Then the separated catalyst was recharged with fresh substrate for the next run under the same reaction conditions. General procedure for the Hg poisoning experiments. 7 4-iodoanisole 6a ( mmol), phenylboronic acid 7a (.5 mmol), GPT-Pd catalyst 5c (0.025 mol%) and K2CO3 (.5 mmol) was added to 3 ml water and was heated under air in an oil bath at 80 o C. After 20 min, a mercury droplet was added to the reaction mixture. an immediate suppression of activity was noted, pointing to the heterogeneous nature of the present system. Table S. Mizoroki-Heck Reaction with GPT-Pd 5 in various solvents [a] entry catalyst solvent yield [b] (%) 5a H2O b H2O c H2O d H 2O e H2O c DMF c DMSO c DMSO-H2O(:2) 9 9 5c DMSO-H2O(:) 95 4

5 0 5c DMSO-H2O(3:) 95 [a] Reaction conditions: 6a (0.5 mmol), 9a (0.6 mmol), Et3N (.5 mmol), mol% of 5a-e, 3 ml of solvent at 80 o C under air. [b] Yields of isolated products are the average of at least two experiments. Table S2. Sonogashira reaction with GPT-Pd 5c and 5d. [a] Entry Catalyst R Ar Yield [b] (%) 5c 4-CH3 Ph 93(2a) 2 5d 4-CH3 Ph 88(2a) 3 5c 4-OCH3 Ph 95(2b) 4 5d 4-OCH3 Ph 92(2b) 5 5c 4-Cl Ph 87(2c) 6 5d 4-Cl Ph 83(2c) 7 5c 4-NO2 Ph 95(2d) 8 5d 4-NO2 Ph 89(2d) 9 5c 3-NO2 Ph 96(2e) 0 5d 3-NO 2 Ph 9(2e) 5c H pyridine 92(2f) 2 5d H pyridine 90(2f) [a] Reaction conditions: aryl iodides 6 (0.5 mmol), terminal alkynes (0.75 mmol), mol% of 5c and 5d, Et3N (.5 mmol), 3 ml of H2O: DMSO (:) at 80 o C under air. [b] Isolated yield. 3. Characterization of the Products: 4-Pyridyl--(2,3,4,6-tetra-O-acetyl--D-glucopyranosyl)-,2,3-triazole 4a : white solid, 93% yield, mp C. (500 MHz, DMSO):δ 9.00 (s, H), 8.64 (d, J = 4 Hz, H), 8.05 (d, J = 8 Hz, H), 7.93 (td, J = 7.8, 5

6 .5 Hz, H), 7.39 (dd, J = 6.9, 5.3 Hz, H), 6.44 (d, J = 9.2 Hz, H), 5.80 (t, J = 9.4 Hz, H), 5.62 (t, J = 9.5 Hz, H), 5.25 (t, J = 9.8 Hz, H), 4.4 (ddd, J = 0.0, 5.5, 2.4 Hz, H), 4.3 (qd, J = 2.5, 3.9 Hz, 2H), 2.05 (s, 3H), 2.0 (s, 3H),.99 (s, 3H),.82 (s, 3H). 3 C NMR (26 MHz, DMSO):δ 70.55, 70.08, 69.90, 69.4, 50.24, 49.73, 48.3, 37.82, 23.87, 22.76, 20.0, 84.52, 73.70, 72.45, 70.66, 67.95, 62.35, 20.99, 20.89, 20.74, Pyridyl--(2,3,4,6-tetra-O-pivaloyl--D-glucopyranosyl)-,2,3-triazole 4b: white solid, 95% yield, mp C. (500 MHz, DMSO): δ 9.02 (s, H), 8.64 (d, J = 4.3 Hz, H), 8.02 (d, J = 7.8 Hz, H), 7.92 (d, J = 7.4 Hz, H), (m, H), 6.46 (d, J = 9.2 Hz, H), 5.83 (t, J = 9.3 Hz, H), 5.68 (t, J = 9.5 Hz, H), 5.36 (t, J = 9.8 Hz, H), 4.50 (d, J = 0.0 Hz, H), 4.4 (d, J = 2.0 Hz, 2H),.5 (s, 8H),.3 (s, 9H),.07 (s, 9H), 0.84 (s, 9H). 3 C NMR (26 MHz, DMSO) : δ 77.52, 76.85, 76.2, 76.0, 50.23, 48.29, 37.75, 23.79, 22.87, 20.4, 84.92, 74.20, 72.52, 70.7, 67.38, 6.67, 38.79, 38.76, 38.7, 38.56, 27.23, 27., GPT-Pd catalyst 5a: yellow solid 90% yield, (500 MHz, DMSO): δ 9.57 (s, H), 8.33 (td, J = 7.8,. Hz, H), 8.20 (d, J = 7.6 Hz, H), 8.09 (d, J = 5.5 Hz, H), (m, H), (m, H), (m, H), 5.57 (t, J = 9.2 Hz, H), 5.23 (dd, J = 3., 6.4 Hz, H), 4.45 (ddd, J = 0.0, 5.6, 2.2 Hz, 2H), 4.2 (dd, J = 2.6, 5.6 Hz, H), 4.3 (d, J = 2.4 Hz, 2H), 2.05 (s, 3H), 2.03 (s, 3H), 2.00 (s, 3H),.95 (s, 3H),.92 (s, 3H),.83 (s, 3H). 3 C NMR (26 MHz, DMSO) : δ 76.0, 75.95, 70.47, 69.94, 69.82, 69.53, 49.95, 48.0, 47.7, 4.9, 26.62, 24.68, 22.78, 85.98, 74.32, 7.97, 70.75, 67.78, 62.5, 40.58, 40.4, 40.25, 40.08, 39.9, 39.75, 39.58, 6

7 23.77, 23.29, 20.96, 20.82, 20.68, Anal. calcd. for C25H30N4O3Pd: C, 42.84; H, 4.3; N, 7.99; found: C, 42.80; H, 4.4; N, 782. GPT-Pd catalyst 5b: yellow solid 92% yield, (500 MHz, DMSO): δ 9.63 (s, H), 8.33 (s, H), 8.8 (d, J = 7.8 Hz, H), 8.0 (d, J = 5.6 Hz, H), 7.70 (s, H), 6.63 (d, J = 9.0 Hz, H), 5.72 (t, J = 9.6 Hz, H), 5.55 (d, J = 9.2 Hz, H), 5.34 (d, J = 9.9 Hz, H), 4.58 (s, H), 4.8 (d, J = 3.5 Hz, 3H),.92 (s, 3H),.8 (s, 3H),.7 (d, J = 2.5 Hz, H),.2 (s, H),.07 (s, H), 0.99 (d, J = 5. Hz, H). 3 C NMR (26 MHz, DMSO) : δ 77.53, 76.86, 76.20, 76.02, 50.25, 49.80, 48.30, 37.78, 23.82, 22.86, 20.4, 84.89, 74.5, 72.49, 70.68, 67.3, 6.65, 27.23, 27., Anal. calcd. for C37H54N4O3Pd: C, 5.2; H, 6.26; N, 6.45; found: C, 5.8; H, 6.20; N, GPT-Pd catalyst 5c: yellow solid 97% yield, (500 MHz, DMSO): δ 9.69 (s, H), 9.0 (d, J = 5.4 Hz, H), 8.34 (d, J =. Hz, H), 8.8 (d, J = 7.7 Hz, H), 7.76 (s, H), 6.66 (d, J = 9.0 Hz, H), 5.76 (t, J = 9.5 Hz, H), 5.55 (s, H), 5.34 (t, J = 9.8 Hz, H), 4.6 (s, H), 4.9 (d, J = 2.7 Hz, 2H),.8 (s, 9H),.3 (s, 0H),.07 (s, 0H), 0.98 (s, 9H). 3 C NMR (26 MHz, DMSO) : δ 77.50, 76.79, 76.48, 76.6, 5.33, 49.25, 48.0, 42.06, 26.87, 24.82, 23.00, 86.36, 74.58, 7.80, 7.07, 67.09, 6.66, 27.27, 27.9, 27.09, Anal. calcd. for C33H48Cl2N4O9Pd: C, 48.2; H, 5.89; N, 6.82; found: C, 48.3; H, 5.77; N, GPT-Pd catalyst 5d: 7

8 yellow solid 8% yield. (500 MHz, DMSO): δ 9.70 (s, H), 9.24 (s, H), 8.35 (t, J = 7.3 Hz, H), 8.8 (d, J = 7.4 Hz, H), 7.76 (s, H), 6.67 (d, J = 8.8 Hz, H), 5.75 (t, J = 9.3 Hz, H), 5.56 (t, J = 9.0 Hz, H), 5.35 (t, J = 9.7 Hz, H), 4.60 (d, J = 9.6 Hz, H), 4.9 (s, 2H),.8 (s, 9H),.3 (s, 9H),.07 (s, 9H), 0.98 (s, 9H). 3 C NMR (26 MHz, DMSO):δ 77.50, 76.79, 76.48, 76.6, 5.33, 49.25, 48.0, 42.06, 26.87, 24.82, 23.00, 86.36, 74.58, 7.80, 7.07, 67.09, 6.66, 27.27, 27.9, 27.09, Anal. calcd. for C33H48Br2N4O9Pd: C, 43.5; H, 5.3; N, 6.5; found: C, 43.56; H, 5.27; N, GPT-Pd catalyst 5e: yellow solid 78% yield. (500 MHz, DMSO): δ 9.54 (s, H), 9.02 (d, J = 5.6 Hz, H), 8.34 (t, J = 7.7 Hz, H), 8.9 (d, J = 7.7 Hz, H), 7.74 (t, J = 6.6 Hz, H), 5.84 (d, J = 9.2 Hz, H), 5.66 (d, J = 5.6 Hz, H), 5.40 (d, J = 5. Hz, H), 5.24 (d, J = 5.5 Hz, H), 4.68 (t, J = 5.7 Hz, H), 3.73 (ddd, J = 5.0, 0.0, 5.9 Hz, 2H), (m, H), (m, 3H). 3 C NMR (26 MHz, DMSO):δ 50.27, 48.47, 4.92, 26.8, 25.9, 22.54, 89.75, 80.7, 76.64, 73.6, 69.69, 6.08, Anal. calcd. for C3H6Cl2N4O5Pd: C, 32.5; H, 3.32; N,.54; found: C, 32.9; H, 3.28; N,.48. Products of Suzuki-Miyaura reactions: 3 4-methoxybiphenyl 8a: (500 MHz, CDCl3): δ 7.60 (dd, J =.4, 8.2 Hz, 4H), 7.47 (t, J = 7.7 Hz, 2H), 7.36 (t, J = 7.4 Hz, H), 7.03 (d, J = 8.7 Hz, 2H), 3.90 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C3H2O: 84.0, found: 84. 8

9 4-methylbiphenyl 8b: (500 MHz, CDCl3): δ 7.69 (dt, J = 8.2, 4.2 Hz, 2H), 7.59 (d, J = 8. Hz, H), 7.54 (q, J = 7.9 Hz, 2H), (m, H), 7.34 (d, J = 7.9 Hz, 2H), 2.48 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C3H2: 68.0, found: chlorobiphenyl 8c: (500 MHz, CDCl3): δ (m, 4H), 7.42 (m, J = 0.9, 8.5, 4.6 Hz, 4H), 7.35 (t, J = 7.4 Hz, H). GC-MS (EI) [M]+: m/z calcd. For C2H9Cl: 88.0, found: 88. biphenyl-4-ol 8d: (500 MHz, DMSO): δ 9.5 (s, H), 7.58 (dd, J = 8.2,. Hz, 2H), (m, 2H), 7.4 (t, J = 7.7 Hz, 2H), 7.28 (t, J = 7.4 Hz, H). GC-MS (EI) [M]+: m/z calcd. for C2H0O: 70.0, found: nitrobiphenyl 8e: (500 MHz, CDCl3): δ (m, H), (m, H), 7.70 (dd, J = 5.3, 3.3 Hz, H), (m, 0.5H), 7.52 (dt, J = 9.6, 4.3 Hz, 0.5H). GC-MS (EI) [M]+: m/z calcd. for C2H9NO2: 99.0, found: (trifluoromethyl)biphenyl 8f: (500 MHz, CDCl3 ): δ 7.73 (s, H), 7.65 (dd, J = 8.2,.0 Hz, 3H), (m, 3H), (m, H). GC-MS (EI) [M]+: m/z calcd. for C3H9F3: 222.0, found: 222.,':4',''-Terphenyl 8g: 9

10 (500 MHz, CDCl3): δ 7.7 (s, 4H), (m, 4H), 7.46 (t, J = 7.7 Hz, 4H), 7.36 (t, J = 7.4 Hz, 2H). GC-MS (EI) [M]+: m/z calcd. for C4H2O: 96.0, found: 96. biphenyl 8h: (500 MHz, CDCl3): δ (m, 4H), 7.56 (dd, J = 0.5, 4.8 Hz, 4H), (m, 2H). GC-MS (EI) [M]+: m/z calcd. for C2H0: 54.0, found: nitrobiphenyl 8i: (500 MHz, CDCl3): δ 8.48 (t, J =.9 Hz, H), 8.22 (dd, J = 8.2,.4 Hz, H), 7.94 (d, J = 7.8 Hz, H), 7.65 (dt, J = 3.9, 4.7 Hz, 3H), 7.53 (dd, J = 0.3, 4.8 Hz, 2H), (m, H). GC-MS (EI) [M]+: m/z calcd. for C2H9NO2: 99.0, found: methylbiphenyl 8j: (500 MHz, CDCl3): δ 7.60 (dd, J = 8.2,. Hz, H), (m, 3H), (m, 3H), (m, 2H), 2.27 (s, 3H).GC-MS (EI) [M]+: m/z calcd. for C3H2: 68.0, found: methoxy-4'-(trifluoromethoxy)biphenyl 8k: (500 MHz, CDCl3): δ 7.68 (dd, J = 9., 2.4 Hz, 2H), (m, 2H), (m, 2H), 3.88 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C4HF3O2: 268.0, found:

11 4,4'-dimethoxybiphenyl 8l: (500 MHz, CDCl3): δ (m, 4H), (m, 4H), 3.87 (s, 6H). GC-MS (EI) [M]+: m/z calcd. for C4H4O2: 24.0, found: methoxy-4'-methylbiphenyl 8m: (500 MHz, CDCl3): δ 7.55 (dd, J = 9.3, 2.5 Hz, 2H), 7.49 (d, J = 8. Hz, 2H), 7.26 (d, J = 7.9 Hz, 2H), 7.00 (dd, J = 9.3, 2.5 Hz, 2H), 3.87 (s, 3H), 2.4 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C4H4O: 98.0, found: 98. 2,4'-dimethoxybiphenyl 8n: (500 MHz, CDCl3): δ (m, 2H), (m, 2H), 7.0 (td, J = 7.5, 0.9 Hz, H), (m, 3H), 3.90 (s, 3H), 3.87 (s, 3H) GC-MS (EI) [M]+: m/z calcd. for C4H4O2: 24.0, found: fluoro-4'-methoxybipheny 8o: l (500 MHz, CDCl3): δ (m, 4H), (m, 2H), (m, 2H), 3.87 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C3HFO: 202.0, found: tert-butyl-4'-methoxybiphenyl 8p: (500 MHz, CDCl3): δ (m, 4H), (m, 2H), (m, 2H), 3.89 (s, 3H),.40 (s, 9H). GC-MS (EI) [M]+: m/z calcd. for C7H20O: 240.0, found: 240.

12 4'-methoxybiphenyl-4-ol 8q: (500 MHz, CDCl3): δ (m, 2H), (m, 2H), (m, 2H), (m, 2H), 3.87 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C3H2O2: 200.0, found: '-methoxy-3-methylbiphenyl-4-amine 8r: (500 MHz, CDCl3): δ (m, 2H), 7.00 (dd, J = 6.7, 2. Hz, 4H), 6.79 (d, J = 7.9 Hz, H), 4.0 (dd, J = 6.2, 43.2 Hz, 2H), (m, 3H), 2.32 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C4H2O: 96.0, found: 96 2-(4-methoxyphenyl)thiophene 8s: (500 MHz, CDCl3): δ (m, 2H), (m, 2H), 7.5 (dd, J = 5., 3.6 Hz, H), (m, 2H), 3.86 (s, 3H).GC-MS (EI) [M]+: m/z calcd. for CH0OS: 90.0, found: 90. -(4'-fluorobiphenyl-4-yl)ethanone 8t: (500 MHz, CDCl3): δ (m, 2H), (m, 2H), 7.29 (2H), (m, 2H), 2.66 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C4H2O: 96.0, found: 96 4'-tert-butyl-2-nitrobiphenyl 8u: (500 MHz, CDCl3): δ 8.55 (t, J =.9 Hz, H), (m, H), (m, H), (m, 3H), (m, 2H),.48 (s, 9H). 2

13 GC-MS (EI) [M]+: m/z calcd. for C4H2O: 96.0, found: 96. 4'-methoxybiphenyl-2-amine 8v: (500 MHz, CDCl3): δ 7.42 (dd, J = 6.7, 4.8 Hz, 2H), (m, 2H), (m, 4H), 5.04 (br, 2H), 3.84 (d, J = 4.3 Hz, 3H). GC-MS (EI) [M]+: m/z calcd. for C3H3NO: 99.0, found: (4-fluorophenyl)thiophene 8w: (500 MHz, CDCl3): δ (m, 2H), 7.3 (dd, J = 5.,.0 Hz, H), (m, H), (m, 3H). 3 C NMR (26 MHz, CDCl3) : δ 63.33, 6.37, 43.30, 30.63, 27.97, 27.67, 24.64, 22.97, 5.74, 5.6. Products of Mizoroki-Heck reaction reactions: 4 (E)-,2-diphenylethene 0a: (500 MHz, CDCl3): δ 7.58 (d, J = 7.5 Hz, 4H), 7.43 (dd, J = 9.8, 5.5 Hz, 4H), (m, 2H), 7.8 (d, J =.3 Hz, 2H).GC-MS (EI) [M]+: m/z calcd. for C4H2: 80.0, found: 80. (E)--methyl-4-styrylbenzene 0b: (500 MHz, CDCl3): δ (m, 2H), (m, 2H), (m, 2H), 7.32 (dd, J = 8.3, 5.4 Hz, H), (m, 2H), (m, 2H), (m, 3H).GC-MS (EI) [M]+: m/z calcd. for C5H4: 94.0, found: 94. (E)--nitro-4-styrylbenzene 0c: 3

14 (500 MHz, CDCl3): δ 8.24 (d, J = 8.8 Hz, 2H), 7.65 (d, J = 8.7 Hz, 2H), 7.58 (d, J = 7.3 Hz, 2H), 7.43 (t, J = 7.5 Hz, 2H), (m, H), 7.29 (t, J = 4.4 Hz, H), 7.7 (d, J = 6.3 Hz, H). GC-MS (EI) [M]+: m/z calcd. for C4HNO2: 225.0, found: 225. (E)--chloro-4-styrylbenzene 0d: (500 MHz, CDCl3): δ 7.55 (d, J = 7.4 Hz, 2H), 7.46 (t, J = 9.4 Hz, 2H), 7.4 (t, J = 7.6 Hz, 2H), 7.37 (d, J = 8.5 Hz, 2H), 7.33 (t, J = 7.3 Hz, H), (m, 2H).GC-MS (EI) [M]+: m/z calcd. for C4HCl: 24.0, found: 24. (E)-4-styrylphenol 0e: (500 MHz, DMSO): δ 9.55 (d, J = 2.0 Hz, H), 7.54 (d, J = 7.3 Hz, 2H), (m, 2H), 7.35 (t, J = 7.7 Hz, 2H), (m, H), (m, H), 7.02 (d, J = 6.4 Hz, H), (m, 2H). GC-MS (EI) [M]+: m/z calcd. for C4H2O: 96.0, found: 96. (E)--methoxyl-4-styrylbenzene 0f: (500 MHz, CDCl3): δ (m, 4H), 7.33 (dd, J = 0.6, 4.7 Hz, 2H), 7.2 (t, J = 3.7 Hz, H), 7.05 (d, J = 6.3 Hz, H), 6.96 (d, J = 6.3 Hz, H), (m, 2H), 3.80 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C5H4O: 20.0, found: 20. Methyl cinnamate 0g: 4

15 (500 MHz, CDCl3): δ 7.72 (d, J = 6.0 Hz, H), (m, 2H), (m, 3H), 6.47 (d, J = 6.0 Hz, H), 3.83 (s, 3H).GC-MS (EI) [M]+: m/z calcd. for C0H0O2: 62.0, found: 62. Products of Sonogashira reaction reactions: 5 -methyl-4-(phenylethynyl)benzene 2a: (500 MHz, CDCl3 ): δ 7.58 (dd, J = 7.8,.7 Hz, 2H), 7.48 (d, J = 8. Hz, 2H), 7.38 (dd, J = 5.6, 3.8 Hz, 3H), 7.20 (d, J = 7.9 Hz, 2H), 2.42 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C5H2: 92.0, found: 92. -methoxy-4-(phenylethynyl)benzene 2b: (500 MHz, CDCl3): δ 7.55 (dd, J = 7.8,.4 Hz, 2H), (m, 2H), (m, 3H), 6.92 (t, J = 5.7 Hz, 2H), 3.86 (s, 3H). GC-MS (EI) [M]+: m/z calcd. for C5H2O: 208.0, found: chloro-4-(phenylethynyl)benzene 2c: (500 MHz, CDCl3 ): δ 7.57 (dd, J = 6.5, 3. Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 7.39 (dd, J = 5.0,.8 Hz, 3H), 7.36 (d, J = 8.4 Hz, 2H). GC-MS (EI) [M]+: m/z calcd. for C4H9Cl: 22.0, found: 22. -nitro-4-(phenylethynyl)benzene 2d: 5

16 (500 MHz, CDCl3): δ (m, 2H), (m, 2H), (m, 2H), (m, 3H). GC-MS (EI) [M]+: m/z calcd. for C4H9NO2: 223.0, found:223. -nitro-3-(phenylethynyl)benzene 2e: (500 MHz, CDCl3): δ (m, H), 8.20 (ddd, J = 8.3, 2.3,.0 Hz, H), (m, H), 7.57 (ddd, J = 7.5,., 5.2 Hz, 3H), (m, 3H). GC-MS (EI) [M]+: m/z calcd. for C4H9NO2: 223.0, found: ((3-nitrophenyl)ethynyl)pyridine 2f: (500 MHz, CDCl3): δ 8.67 (d, J = 4.8 Hz, H), 8.45 (d, J =.6 Hz, H), (m, H), 7.92 (d, J = 7.7 Hz, H), 7.77 (td, J = 7.7,.7 Hz, H), 7.58 (dd, J = 6.8, 8.5 Hz, 2H), (m, H). GC-MS (EI) [M]+: m/z calcd. for C3H8N2O2: 224.0, found: 224. Quinolone bromides: HNMR (500 MHz, CDCl3) δ 8.68 (s, H), 7.57 (d, J = 8.9 Hz, H), (m, H), 4.64 (d, J =.9 Hz, H), 4.49 (d, J = 2.3 Hz, H), 4.24 (dd, J = 7., 4.0 Hz, 2H),.42 (d, J = 6.8 Hz, 3H),.30 (t, J = 7. Hz, 3H). 3 C NMR (26 MHz, 6

17 DMSO) δ 72.5, 65.04, 55.39, 46.47, 45.03, 28.65, 23.48, 0.08, 03.4, 0.56, 68.86, 60.34, 53.25, 8.39, 4.6. Novel fluoroquinolone derivatives: (500 MHz, CDCl3) δ 8.40 (s, H), 7.80 (dd, J = 5.0, 7.0 Hz, H), 7.69 (dd, J = 7.8, 4.2 Hz, H), 7.55 (ddd, J = 25.2, 5.6, 6.5 Hz, H), 7.47 (dd, J = 7.2, 2.8 Hz, H), (m, 2H), 6.80 (t, J = 2.2 Hz, 2H), (m, 3H), 4.36 (s, 2H),.60 (d, J = 6.7 Hz, 3H),.44 (t, J = 7. Hz, 3H). 3 C NMR (26 MHz, CDCl3) δ 72.8, 65.86, 56.77, 44.98, 32.29, 30.45, 29.28, 28.34, 23.68, 5.08, 4.99, 0.80, 05.07, 68.3, 60.87, 54.85, 34.56, 29.38, 23.22, 7.93,

18 3.Copies of NMR and GC-MS Spectra 4. Figure S. 2D ROESY NMR spectrum of Pd catalyst 5c. Figure S2. XPS analysis of GPT-Pd catalyst 5c (blue for before and red for after the reaction.) 8

19 Figure S3. Thermo-gravimetric analysis graphs of GPT-Pd catalysts 5a-d 9

20 4a 3 C NMR 4a 20

21 4b 3 C NMR 4b 2

22 5a 3 C NMR 5a 22

23 5b 3 C NMR 5b 23

24 5c 3 C NMR 5c 24

25 HNMR 5d 3 C NMR 5d 25

26 5e 3 C NMR 5e 26

27 8a 8b 27

28 8c 8d 28

29 8e 8f 29

30 8g 8h 30

31 8i 8j 3

32 8k 8l 32

33 8m 8n 33

34 O F 8o 8p 34

35 8q 8r 35

36 8s 8t 36

37 8u 8v 37

38 8w 3 C NMR 8w 38

39 0a 0b 39

40 0c 0d 40

41 0e 0f 4

42 0g 2a 42

43 2b 2c 43

44 2d 2e 44

45 2f Quinolone bromides: 45

46 46

47 The selected GC-MS chromatogram of products: 4-methoxybiphenyl 8a: GC-MS (EI) [M]+: m/z calcd. for C3H2O: 84.0, found:

48 4-methylbiphenyl 8b: GC-MS (EI) [M]+: m/z calcd. for C3H2: 68.0, found: chlorobiphenyl 8c: GC-MS (EI) [M]+: m/z calcd. for C2H9Cl: 88.0, found:

49 biphenyl-4-ol 8d: GC-MS (EI) [M]+: m/z calcd. for C2H0O: 70.0, found: nitrobiphenyl 8e: GC-MS (EI) [M]+: m/z calcd. for C2H9NO2: 99.0, found:

50 4-(trifluoromethyl)biphenyl 8f: GC-MS (EI) [M]+: m/z calcd. for C3H9F3: 222.0, found: nitrobiphenyl 8h: GC-MS (EI) [M]+: m/z calcd. for C2H9NO2: 99.0, found:

51 2-methylbiphenyl 8j: GC-MS (EI) [M]+: m/z calcd. for C3H2: 68.0, found: methoxy-4'-(trifluoromethoxy)biphenyl 8k: 5

52 GC-MS (EI) [M]+: m/z calcd. for C4HF3O2: 268.0, found: ,4'-dimethoxybiphenyl 8l: GC-MS (EI) [M]+: m/z calcd. for C4H4O2: 24.0, found:

53 4-methoxy-4'-methylbiphenyl 8m: GC-MS (EI) [M]+: m/z calcd. for C4H4O: 98.0, found: 98. 2,4'-dimethoxybiphenyl 8n: GC-MS (EI) [M]+: m/z calcd. for C3HFO: 202.0, found: 202. (E)-,2-diphenylethene 0a: GC-MS (EI) [M]+: m/z calcd. for C4H2: 80.0, found:

54 E)--methyl-4-styrylbenzene 0b: GC-MS (EI) [M]+: m/z calcd. for C5H4: 94.0, found: 94. (E)--nitro-4-styrylbenzene 0c: GC-MS (EI) [M]+: m/z calcd. for C4HNO2: 225.0, found:

55 (E)--chloro-4-styrylbenzene 0d: GC-MS (EI) [M]+: m/z calcd. for C4HCl: 24.0, found: 24. (E)--methoxyl-4-styrylbenzene 0f: GC-MS (EI) [M]+: m/z calcd. for C5H4O: 20.0, found:

56 Methyl cinnamate 0g: GC-MS (EI) [M]+: m/z calcd. for C0H0O2: 62.0, found:

57 The selected GC-analysis of products: calibration curve [General procedure: 分别将产物标准溶液稀释成 20 mg/0 ml, 40 mg/0 ml, 60 mg/0 ml, 80 mg/0 ml, 00 mg/0ml 的梯度质量浓度, 取梯度质量浓度的产物标准溶液 00 μl 于 20 ml 试管中, 加人 500 μl 22.6 mg/0 ml 内标溶液, 气相色谱测定以产物的峰面积与内标物的峰面积比 ( A 产物 /A 内标 ) 为纵坐标 Y, 其质量比 ( M 产物 /M 内标 ) 为横坐标 X, 绘制标准曲线 ] NO average Si/s response factor:si/s = Si/Ss = Ai ms /(As mi) Si/s= relative quality correcting factor:f i/ s = f i/f s = mias/(msai) mi =(Ai /As)*m s * f i/f s = (Ai /As )*m s / Si/s = *84/ =

58 NO. : NO. 2: NO.3: 58

59 NO.4: NO.5: 59

60 Table, entry 5, 84% of GC yield: Table, entry 6, 99% of GC yield: 60

61 4. X-ray Crystal Data for GPT-Pd catalyst 5c Crystals of GPT-Pd catalyst 5c (C33H48Cl2N4O9Pd) were recrystallized from a acetonitrile-dichloromethane solution. A single white needle crystal which was suitable for X-ray diffraction measurements was mounted on a glass fiber. Unit cell measurements and intensity data collections were performed on a Rigaku AFC7R diffractometer with graphite monochromated Mo Ka. The data reduction included a correction for Lorentz and polarization effects, with an applied multi-scan absorption correction (SADABS). The crystal structure was solved and refined using the SHELXTL- 97 program suite. Direct methods yielded all non-hydrogen atoms which were refined with anisotropic thermal parameters. The reflection data were consistent with a monoclinic system: P2()/c. The obtained crystal structure has been deposited at the Cambridge Crystallographic Data Centre and allocated the deposition number: (CCDC NO). The crystallographic data and refinement parameters of 5c are listed in Table S. 6

62 Table S. Crystallographic data and structure refinement for 5c. Identification code 4044_cc204_2_b Empirical formula C66 H96Cl4 N8 O8 Pd2 Formula weight 644. Temperature, K 293(2) K Wavelength, Å Å Crystal system Orthorhombic Space group P222 Cell dimensions a, b, c, Å (3) Å,.4036(5) Å, (5)Å α, β, γ, o 90 o, 90 o, 90 o Volume, Å (3) Å 3 Z 2 Calculated density, g/cm 3.85 Absorption coefficient, mm F (000) 704 Crystal size, mm 0.32 x 0.28 x 0.6 mm Theta range for data collection, o 3.03 to 25.0 deg Limiting indices -0<=h<=, -3<=k<=0, -47<=l<=49 Completeness to theta = 25.0 o 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 808 / 64 / 465 Goodness of fit on F 2.40 R indices [I > 2σ(I)] R = , wr2 = R indices (all data) R = , wr2 = Absolute structure parameter 0.02(5) Largest diff. peak and hole, e Å and e.a^-3 62

63 6.References. a) C. Shen, H. Zheng, P. Zhang, X. Chen, J. Carbohydr. Chem. 200, 29, 55-63; b)c. Shen, H. Xia, H. Yan, X. Chen, S. Ranjit, X. Xie, D. Tan, R. Lee, Y. Yang, B. Xing, K.-W. Huang, P. Zhang, X. Liu, Chem. Sci. 202, 3, a) S. Santra, P. K. Hota, R. Bhattacharyya, P. Bera, P. Ghosh, S. K. Mandal, ACS Catal. 203, 3, ; b)w. Susanto, C.-Y. Chu, W. J. Ang, T.-C. Chou, L.-C. Lo, Y. Lam, Green Chem. 202, 4, a) C. Liu, Y. Zhang, N. Liu, J. Qiu, Green Chem. 202, 4, ; b) L. Liu, Y. Dong, N. Tang, Green Chem. 204, 6, ; c)q.zhang, H. Su, J. Luo, Y. Wei, Catal. Sci. Technol. 203, 3, a) M.Gopiraman, R. Karvembu, I. S Kim, ACS Catal. 204, 4 (7), ; b) F.Chen, M.Huang, Y.Li, Ind. Eng. Chem. Res. 204, 53 (20), a) M. Planellas, Y. Moglie, F. Alonso, M. Yus, R. Pleixats, A. Shafir, Eur. J. Org. Chem. 204, 204, ; b) A. Modak, J. Mondal, A. Bhaumik, Green Chem. 202, 4 (0), Q. Wang, E. Lucien, A. Hashimoto, G. C. G. Pais, D. M. Nelson, Y. Song, J. A. Thanassi, C. W. Marlor, C. L. Thoma, J. Cheng, S. D. Podos, Y. Ou, M. Deshpande, M. J. Pucci, D. D. Buechter, B. J. Bradbury, J. A. Wiles, J. Med. Chem. 2007, 50, R. H. Crabtree, Chem Rev. 202, 2,

64 64