<p>Supporting Information</p><p>Title: An easily prepared tetraphosphine and its use in the palladium-catalyzed Suzuki-Miyaura</p><p> coupling of aryl chlorides</p><p>Authors: Kun Wang, Wei Wang, Heng Luo, Xueli Zheng, Haiyan Fu, Hua Chen, Ruixiang Li*</p><p>General experimental details: </p><p>Reactions were carried out under a nitrogen atmosphere. All chemicals were purchased from</p><p> commercial suppliers. [Ph2P(CH2OH)2]Cl was prepared according to the reported methods [1].</p><p>Solvents were dried over appropriate drying agents and distilled under argon before use. Reagent- grade reactants were used directly without further purification. Chromatographic separations were performed using standard column methods with silica gel (300-400 mesh). NMR spectra were recorded on a Bruker Avance II-400 MHz with reference to TMS as the internal standard. Gas chromatograph analysis was performed on an Agilent GC 6890 N with an SE-30 column of 30 m×0.32 mm ×0.25 μm. High-resolution mass spectra were recorded on a Q-TOF mass spectrometry equipped with Z-spray ionization source.</p><p>Synthesis of N,N,N′,N′-tetra(diphenylphosphinomethyl)-1,2-ethylenediamine (L1)</p><p>Excess of triethylamine (3 mL, 20 mmol) was added to a solution of [PPh2(CH2OH)2]Cl (2.8 g, 10 mmol) in water-methanol (1:2, 30 mL), then this solution was added to 1,2-ethylenediamine (138 μL, 2 mmol). The mixture was refluxed for 30 h. At the end of reaction, the product was extracted with dichloromethane (2×10 mL), dried over magnesium sulfate and filtered. Subsequently, the dichloromethane solution was reduced to ca 1-2 mL under vacuum, and ethanol of 20 ml was added into it to give white precipitate. The precipitate was filtered, washed with ethanol, and dried under</p><p>31 vacuum to give the product as a white powder (1.4 g, 91% yield). P NMR (162 MHz, CDCl3): δ -28.4</p><p>1 ppm. H NMR (400 MHz, CDCl3): δ 7.37-7.23 (m, 40H), 3.50 (d, 8H), 2.88 (s, 4H). </p><p>Synthesis of N,N,N′,N′-tetra(diphenylphosphinomethyl)-cyclohexane-1,2-diamine (L2)</p><p>Excess of triethylamine (3 mL, 20 mmol) was added to a solution of [PPh2(CH2OH)2]Cl (2.8 g, 10 mmol) in water-ethanol (2:1, 50 mL), then this solution was added to 1,2-cyclohexanediamine (246</p><p>μL, 2 mmol). The mixture was refluxed for 30 h. At the end of reaction, the product was extracted with dichloromethane (2×10 mL), dried over magnesium sulfate and filtered. Subsequently, the dichloromethane solution was reduced to ca 1-2 mL under vacuum, and ethanol of 20 ml was added into it to give white precipitate. The precipitate was filtered, washed with ethanol, and dried under</p><p>31 vacuum to give the product as a white powder (1.3 g, 75% yield). P NMR (162 MHz, CDCl3): δ</p><p>1 -24.82, -24.56 ppm. H NMR (400 MHz, CDCl3): δ 7.68-7.07 (m, 40H), 3.55-3.64 (m, 8H), 2.93 (d,</p><p>2H), 1.61-1.01 (m, 8H). </p><p>Characterization data for the catalytic products</p><p>All the catalytic products are known compounds and they were characterized by comparing their 1H</p><p>NMR spectra with those reported previously.</p><p>4-Methoxybiphenyl (Table 3, entry 1): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[2].</p><p>4-Acetylbiphenyl (Table 3, entries 2,3): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[3].</p><p>2-Acetylbiphenyl (Table 3, entries 4,5): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[4].</p><p>4-Nitrobiphenyl (Table 3, entries 6,7): Yellow solid. The 1H NMR spectra was identical to that previously reported in Ref.[3].</p><p>2-Nitrobiphenyl (Table 3, entries 8,9): Yellow solid. The 1H NMR spectra was identical to that previously reported in Ref.[4].</p><p>4-Trifluoromethylbiphenyl (Table 3, entries 10,11): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[3].</p><p>4-Phenylbenzonitrile (Table 3, entries 12,13): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[3].</p><p>2-Phenylbenzonitrile (Table 3, entries 14,15): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[4].</p><p>4-Biphenylaldehyde (Table 3, entries 16,17): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[4].</p><p>2-Biphenylaldehyde (Table 3, entry 18): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[5].</p><p>2-Nitro-4-(trifluoromethyl)-1,1'-biphenyl (Table 3, entries 19-23): Yellow solid. The 1H NMR spectra was identical to that previously reported in Ref.[6].</p><p>References</p><p>[1] Fawcett J, Hoye PAT, Kemmitt RDW (1993) J Chem Soc Dalton Trans:2563.</p><p>[2] Seganish WM, DeShong P (2004) Org Lett 6:4379. [3] Song C, Ma Y-D, Chai Q, Ma C-Q, Jiang W, Andrus MB (2005) Tetrahedron 61:7438.</p><p>[4] Zhou W-J, Wang K-H, Wang J-X (2009) J Org Chem 74:5599.</p><p>[5] Desmarets C, Omar-Amrani R, Walcarius A, Lambert J, Champagne B, Fort Y, Schneider R (2008) </p><p>Tetrahedron 64:372.</p><p>[6] Freeman AW, Urvoy M, Criswell ME (2005) J Org Chem 70:5014.</p><p>31 P NMR (162 MHz, CDCl3) 1H NMR (400 MHz, DMSO)</p><p>13 C NMR (101 MHz, CDCl3) 14:45:08 27-Oct-2011 111027_WK1024 12 (0.205) AM (Cen,4, 80.00, Ar,10000.0,0.00,0.70); Sm (SG, 2x3.00); Cm (1:59) TOF MS ES+ 901.3155 1.52e3 100</p><p>902.3143 %</p><p>899.2991</p><p>903.3184 955.3162</p><p>764.1660 925.2981 956.3200 940.1436 779.2036 957.3259 1045.2516 782.1380 845.0789 891.3478 994.1297 1075.3783 785.2208 831.1053 972.1109 1089.3274 1022.2057 1112.3419 1143.3309 1194.1791 0 m/z 760 780 800 820 840 860 880 900 920 940 960 980 1000 1020 1040 1060 1080 1100 1120 1140 1160 1180</p><p>HRMS (ESI)</p>