Supporting Information s50

Supporting Information

Title: An easily prepared tetraphosphine and its use in the palladium-catalyzed Suzuki-Miyaura

coupling of aryl chlorides

Authors: Kun Wang, Wei Wang, Heng Luo, Xueli Zheng, Haiyan Fu, Hua Chen, Ruixiang Li*

General experimental details:

Reactions were carried out under a nitrogen atmosphere. All chemicals were purchased from

commercial suppliers. [Ph2P(CH2OH)2]Cl was prepared according to the reported methods [1].

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.

Synthesis of N,N,N′,N′-tetra(diphenylphosphinomethyl)-1,2-ethylenediamine (L1)

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

31 vacuum to give the product as a white powder (1.4 g, 91% yield). P NMR (162 MHz, CDCl3): δ -28.4

1 ppm. H NMR (400 MHz, CDCl3): δ 7.37-7.23 (m, 40H), 3.50 (d, 8H), 2.88 (s, 4H).

Synthesis of N,N,N′,N′-tetra(diphenylphosphinomethyl)-cyclohexane-1,2-diamine (L2)

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

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

31 vacuum to give the product as a white powder (1.3 g, 75% yield). P NMR (162 MHz, CDCl3): δ

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,

2H), 1.61-1.01 (m, 8H).

Characterization data for the catalytic products

All the catalytic products are known compounds and they were characterized by comparing their 1H

NMR spectra with those reported previously.

4-Methoxybiphenyl (Table 3, entry 1): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[2].

4-Acetylbiphenyl (Table 3, entries 2,3): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[3].

2-Acetylbiphenyl (Table 3, entries 4,5): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[4].

4-Nitrobiphenyl (Table 3, entries 6,7): Yellow solid. The 1H NMR spectra was identical to that previously reported in Ref.[3].

2-Nitrobiphenyl (Table 3, entries 8,9): Yellow solid. The 1H NMR spectra was identical to that previously reported in Ref.[4].

4-Trifluoromethylbiphenyl (Table 3, entries 10,11): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[3].

4-Phenylbenzonitrile (Table 3, entries 12,13): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[3].

2-Phenylbenzonitrile (Table 3, entries 14,15): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[4].

4-Biphenylaldehyde (Table 3, entries 16,17): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[4].

2-Biphenylaldehyde (Table 3, entry 18): White solid. The 1H NMR spectra was identical to that previously reported in Ref.[5].

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].

References

[1] Fawcett J, Hoye PAT, Kemmitt RDW (1993) J Chem Soc Dalton Trans:2563.

[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.

[4] Zhou W-J, Wang K-H, Wang J-X (2009) J Org Chem 74:5599.

[5] Desmarets C, Omar-Amrani R, Walcarius A, Lambert J, Champagne B, Fort Y, Schneider R (2008)

Tetrahedron 64:372.

[6] Freeman AW, Urvoy M, Criswell ME (2005) J Org Chem 70:5014.

31 P NMR (162 MHz, CDCl3) 1H NMR (400 MHz, DMSO)

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

902.3143 %

899.2991

903.3184 955.3162

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

HRMS (ESI)