Electronic Supporting Information - 英国皇家化学会

Electronic Supporting Information - 英国皇家化学会 Supplementary Material (ESI) for Chemical Communications This journal is ? The Royal Society of Chemistry 2001 Electronic Supplementary Information Experimental Section General procedures. Ether and tetrahydrofuran (THF) for use on vacuum line were distilled from sodium/benzophenone in a nitrogen atmosphere. (R)- and (S)-1,1'-binaphthyl-2,2’-diols (99 % ee) were obtained from Aldrich. Rac-1,1'-binaphthyl-2,2’- diol was prepared by oxidation 2-naphthol with FeCl in water (K. Ding, Y. Wang, L. 3 Zhang, Y. Wu, T. Matsuura, Tetrahedron 1996, 52, 1005). (R)-, (S)-, and rac-6,6'- dibromo-1,1'-binaphthyl-2,2’-diol (3) were prepared from the corresponding 1,1'- binaphthyl-2,2’-diols, as described previously (J. Cuntze, L. Owens, V. Alcazar, P. Seiler, F. Diedrich, Helv. Chim. Acta 1995, 78, 367). Other major chemicals were obtained from Aldrich or Acros. Column chromatography was carried on TLC or flash grade silica gel (Aldrich), using 10 – 20 psig pressure. 1NMR spectra were obtained using Omega and Bruker spectrometers (H, 500 1MHz and 300 MHz) in CDCl; the chemical shift references were as follows: (H) TMS, 3 130.0 ppm (CDCl); (C) CDCl, 77.0 ppm (CDCl). For selected spectra, exponential 333 (EM) and Gaussian (GB) multiplication prior to the Fourier transform was employed. (The exponents were shown in Hz.) IR spectra were obtained using the FT instrument Analect RFX-30 operating in ATR mode. A few drops of the compound in CHCl were applied to the surface of a 22 ZnSe ATR plate parallelogram (45:, Wilmad), and after the solvent evaporated, the -1spectrum was acquired (32 scans, 2-cm resolution). UV-vis absorption spectra were recorded at ambient temperature in 10-mm-path-length quartz cells using a Hewlett Packard 8450A spectrophotometer. Optical rotations were measured with Autopol III (Rudolph Research) at ambient temperature. Elemental analyses were carried out by M-H-W Laboratories, P.O. Box 15149, Phoenix, Arizona 85060. X-ray Crystallography. Crystals of rac-1 were grown from hexane/chloroform solution by evaporation of solvent. Diffraction data were collected by the oscillation 1 Supplementary Material (ESI) for Chemical Communications This journal is ? The Royal Society of Chemistry 2001 method using a Bruker AXS molybdenum-target rotating anode X-ray source and an 18 cm MARResearch imaging plate detector. The program MARXDS (W. Kabsch, J. Appl. Crystallogr., 1988, 21, 916) was used for indexing and integration of the data set. In all, 22523 reflections (6481 unique- R=0.0378) were recorded to a resolution of 0.95 Å. int The phase problem was solved by direct methods using SHELXS97 (G. M. Sheldrick, SHELXL97. Program for the Refinement of Crystal Structures. University of Göttingen, Germany, 1997). This solution contained all but a few of the atoms in the molecule, all of which were located at the ends of the alkoxy chains. The remaining atoms were easily 2located by difference methods (F – F). Least-squares refinement on F of 668 oc parameters was carried out using SHELXL97 and converged to a final R=0.0691, wR= 12 0.1630, and GOF = 1.333 for 4598 reflections with F> 4,(F). Hydrogen atoms were oo generated geometrically and were fixed in a riding model. All non-hydrogen atoms were refined anisotropically. A final difference electron density map showed no distinct -3features with , = 0.497 and , = -0.400 e?Å. Further details are in the main text maxmin and the deposited CIF. 2’-bithiophene (2). n-BuLi (2.85 M in hexane, 47.9 mL, 5’-Bromo-5-phenyl-2, 0.137 mol, 1.1 equiv) was added dropwise to 2,5-dibromothiophene (13.9 mL, 30.0 g, 0.124 mol) in ether (700 mL) at –78 :C. After 2 h at –78 :C, solid CuCl (50.0 g) was 2 added under nitrogen gas flow to the stirred reaction mixture at –78 :C. Subsequently, the reaction mixture was allowed to attain ambient temperature overnight. Following addition of ice water (1.2 L) and extraction with CHCl (3 x 1.5 L), the combined organic 3 layer was washed with HCl (1.5 L, 15 %), NaHCO (1.2 L), and then water (1.5 L). aq3aq After drying of the organic layer over MgSO, evaporation of solvent gave 35.9 g of 5,5’-4 9dibromo-2,2’-bithiophene as a yellow solid, m.p. 141 – 143 :C (lit. m.p. 145 - 146 :C). 1H NMR (500 MHz, CDCl): , 6.96 (d, J = 4, 2H), 6.85 (d, J = 4, 2H). 3 2 Supplementary Material (ESI) for Chemical Communications This journal is ? The Royal Society of Chemistry 2001 Phenylboronic acid (1.280 g, 10.5 mmol), 5,5’-dibromo-2,2’-bithiophene (6.720 g, 20.74 mmol), Ba(OH),8HO (3.307 g, 10.5 mmol) and Pd(PPh) (0.242 g, 0.21 mmol, 2 2234 mol % per bond) in toluene/MeOH (120 mL, 1:1) were heated in a pressure tube under N at 100:C overnight. The brown solution was quenched by adding 200 mL of water 2 and was extracted with CHCl (3 x 200 mL). The combined organic layer was washed 3 with HCl (200 mL, 15 %), NaHCO (200 mL), and water (200 mL), and then dried aq3aq over MgSO. Removal of solvents in vacuo gave 17.790 g of yellow solid. Purification 4 by column chromatography (flash silica, hexane) gave the product 2 as a yellow solid: 1012.29 g, 68 %, m.p. 148 – 149 :C (lit. m.p. 128 – 130 :C). H NMR (500 MHz, CDCl): 3 , 7.585 (dd, J = 8, J = 1, 2H), 7.383 (t, J = 8, 2H), 7.291 (tt, J = 7, J = 1, 1H), 7.208 (d, J 131= 4, 1H), 7.079 (d, J = 4, 1H), 6.979 (d, J = 4, 1H), 6.935 (d, J = 4, 1H). C{H} DEPT NMR (125 MHz, CDCl): , aromatic quaternary region, expected, 5 resonances; found, 5 3 resonances at 143.7 (q), 138.9 (q), 135.6 (q), 133.9 (q), 110.9 (q); aromatic nonquaternary region, expected, 7 resonances; found, 7 resonances at 130.6, 128.9, 127.7, 125.6, 124.8, +123.7, 123.6. GC-MS(CI): m/z (% RA for m/z = 50 - 550) at (M – Br) 241 (78), 242 ++(100), 243 (97) and at M/(M + H) 320 (45), 321 (53), 322 (52), 323 (50). 6,6’-Dibromo-2,2’-bis(decyloxy)-1,1’-binaphthyl (4). A mixture of 6,6'- dibromo-1,1'-binaphthyl-2,2’-diol (4.18 g, 9.41 mmol), anhydrous KCO (8.46 g, 61.3 23 mmol, 6.5 eq.), and n-decyl iodide (5.7 mL, 27 mmol, 2.8 eq) in dry DMF (160 mL) was ostirred at 100 C overnight (12 h). Subsequently, the reaction mixture was cooled to ambient temperature and the usual aqueous workup was carried out (water, 200 mL and ether 3 x 100 mL). The ether layer was dried over anhydrous MgSO, and, after the 4 removal of solvents in vacuo, yellow solid was obtained. The purification by flash chromotography (silica, hexane/CHCl = 9:1) yielded white crystals (5.9 g, 89 %, m.p. 22 86 – 87 :C) of rac-4. r.t.(R)-4: colorless oil, [,] = +26 (c = 0.020 g/mL, CHCl) D22 r.t.(S)-4: colorless oil, [,] = -27 (c = 0.032 g/mL, CHCl) D22 1H NMR (500 MHz, CDCl): 7.991 (d, J = 2, 2H), 7.823 (d, J = 9, 2H), 7.398 (d, J = 9, 3 2H), 7.253 (dd, J = 2, J = 8, 2H), 6.975 (d, J = 9, 2H), 3.872 - 3.965 (m, 4H), 0.930 - 12 1311.412 (m, 32H), 0.886 (t, J = 7, 6H). C{H} NMR (125 MHz, CDCl): 154.8, 132.6, 3 3 Supplementary Material (ESI) for Chemical Communications This journal is ? The Royal Society of Chemistry 2001 130.2, 129.8, 129.4, 128.4, 127.1, 120.1, 117.2, 116.5, 69.6, 31.9, 29.4, 29.3, 29.1, 25.6, 22.7, 14.1. Rac-, (S)-, and (R)-6,6’-bis(5-phenyl-2,2’-bithiophen-5’-yl)-2,2’-bis(decyloxy)- 1,1’-binaphthyl (1). t-BuLi (1.84 M in pentane, 1.9 mL, 4.2 equiv) was added dropwise to 4 (0.600 g, 0.828 mmol, 1 equiv) in THF (24 mL) in a Schlenk vessel at –78 :C. After 2 h at –78 :C, the yellow homogeneous reaction mixture was treated with ZnCl (1.01 M 2 in ether, 1.8 mL, 2.2 equiv), kept stirring at –78:C for 15 min, and then allowed to attain ambient temperature. Pd(PPh) (0.057 g, 0.050 mmol, 3 mol % per bond) and 2 (0.585 g, 34 1.822 mmol) were added to the reaction mixture in argon-filled glovebox. The Schlenk vessel was capped and the reaction mixture was heated in an oil bath at 100 :C for 24 h. The dark brown mixture was cooled down to ambient temperature and quenched with water (200 mL). Following extraction with CHCl (1000 mL for the racemic product), 3 washing with water, the combined organic layer was dried over MgSO, and then 4 concentrated in vacuo to give 1.032 g crude product. Purification by column chromatography (TLC grade silica gel, hexane/benzene or hexane/chloroform) and, in the case of the racemic product, recrystallization from chloroform or hexane/chloroform, gave the products as yellow or yellow-orange solids. FABMS (3-NBA) cluster: m/z (% ++RA for m/z = 600 – 1500) at M/(M + H), 1046.5 (20), 1047.6 (90), 1048.5 (100), 1049.5 (70), 1050.6 (40), 1051.6 (20); calcd for CHOS: 1047.4 (100), 1048.4 (80), 687124 11049.4 (50), 1050.4 (20), 1051.4 (<10), 1052.4 (<5). H NMR (500 MHz, CDCl): , 3 8.064 (d, J = 2, 2H), 7.951 (d, J = 9, 2H), 7.611 (d, J = 7, 4H), 7.483 (dd, J = 9, J = 2, 2H), 7.431 (d, J = 9, 2H), 7.387 (t, J = 8, 4H), 7.297-7.239 (m, 6H), 7.200-7.173 (m, 6H), 1313.999-3.927 (m, 4H), 1.456-0.907 (m, 32H), 0.855 (t, J = 7, 6H).C{H} DEPT NMR (125 MHz, CDCl): , aromatic quaternary region, expected, 10 resonances; found, 10 3 resonances at 154.9 (q), 143.7 (q), 143.0 (q), 136.9 (q), 136.3 (q), 134.1 (q), 133.6 (q), 129.1 (q), 120.5 (q), 104.4 (q); aromatic nonquaternary region, expected, 12 resonances; found, 12 resonances at 129.4, 128.9, 127.6, 126.2, 125.6, 124.6, 124.3, 124.3, 124.1, 123.8, 123.6, 116.4; aliphatic region, 69.7, 31.9, 29.5, 29.5, 29.4, 29.3, 29.2, 25.7, 22.7, 11114.1. H NMR (500 MHz, CDCl H-H COSY cross-peak in aromatic region): , 8.058 3, (d, J = 2, 2H, 7.476), 7.942 (d, J = 9, 2H, 7.432), 7.603 (d, J = 7, 4H, 7.376, 7.288-7.248), 7.476 (dd, J = 9, J = 2, 2H, 8.058, 7.189), 7.432 (d, J = 9, 2H, 7.942), 7.376 (t, J = 8, 4H, 4 Supplementary Material (ESI) for Chemical Communications This journal is ? The Royal Society of Chemistry 2001 7.603, 7.288-7.248), 7.189 (d, J = 9, 2H, 7.476), 7.166 (d, J = 4, 2H, 7.288-7.248). UV- -1vis (CHCl) , (nm) = 241 and 393 (log , = 4.89 – 4.95). IR (cm): 3067 (Ar-H), 2922, 22max 2849 (CH), 1590 (Ar), 1247 (Ar-O-C). Rac-1: 70 % yield, yellow-orange crystals, m.p. 165 - 166 :C (CHCl), Anal. 3 Calcd. for CHOS,(CHCl): C, 72.65; H, 6.27. Found: C, 72.49; H, 6.35. 68702430.75 (S)-1, 59 % yield, yellow solid, m.p. 123 - 124 :C (hexane/CHCl), 115 - 115.5 3 rt:C (CHCl), [,]= +228 (c = 0.005, THF). 3D rt(R)-1, 67 % yield, yellow solid, m.p. 114.5 -115 :C (CHCl), [,]= -227 (c = 3D 0.01, THF), Anal. Calcd. for CHOS: C, 77.97; H, 6.74. Found: C, 77.35; H, 6.52. 687024 6-(5-Phenyl-2,2’-bithiophen-5’-yl)-2-decyloxynaphthalene (5). t-BuLi (1.84 M in pentane, 0.63 mL, 1.156 mmol, 2.1 equiv) was added dropwise to 6-bromo-2-decyloxynaphthalene (200 mg, 0.550 mmol) in THF (8 mL) in a Schlenk vessel at –78 :C. After 2 h at –78 :C, the yellow precipitate reaction mixture was treated with ZnCl (1.15 2 M in ether, 0.53 mL, 0.610 mmol, 1.1 equiv), kept stirring at –78 :C for 20 min, then, warmed to ambient temperature; a colorless solution was obtained. Pd(PPh) (19.1 mg, 34 0.0165 mmol, 3 % equiv) and 5’-bromo-5-phenyl-2,2’-bithiophene (194.5 mg, 0.605 mmol, 1.1 equiv) were added to the reaction mixture in the argon filled glove box. The Schlenk vessel was capped and the reaction mixture was heated in an oil bath at 100 :C for 30 h. The dark yellow mixture was cooled to ambient temperature and quenched with water (200 mL), and yellow solid was precipitated. Using chloroform (100 mL), the precipitate was extracted in organic phase as a solid. The solid was filtered and dried under vacuo line. 232 mg crude product was obtained. Recrystallization from chloroform gave 149 mg of yellow solid, m.p. 260 - 261 :C (yield, 52 %). Anal. Calcd. For CHOS: C, 77.82; H, 6.91. Found: C, 78.42; H, 6.76. 34362 +MS-EI cluster: m/z (% RA for m/z = 100 – 700) at M, 524.3 (100), 525.3 (62), 526.3 ++1(35); at (M - CH), 384.1 (62). H NMR (500 MHz, CDCl): , 7.953 (s, 1H), 7.742-10203 7.667 (m, 3H), 7.606 (d, J = 8, 2H), 7.377 (t, J = 8, 2H), 7.298 - 7.230 (m, 3H), 7.193 - 7.138 (m, 3H), 7.119 (s, 1H), 4.088 (t, J = 6, 2H), 1.877 - 1.822 (m, 2H), 1.539 - 1.290 1(m, 14H), 0.888 (t, J = 7, 3H). H COSY (cross-peak in aromatic region): , 7.742-7.667 (m, 3H, 7.193 - 7.138), 7.606 (d, J = 8, 2H, 7.377), 7.377 (t, J = 8, 2H, 7.606, 7.298 - 5 Supplementary Material (ESI) for Chemical Communications This journal is ? The Royal Society of Chemistry 2001 7.230), 7.298 - 7.230 (m, 3H, 7.377, 7.193 - 7.138, 7.193 – 7.138), 7.193 - 7.138 (m, 3H, 7.742 - 7.667, 7.298 - 7.230, 7.298 – 7.230). UV-vis (CHCl) : , (nm) = 239 and 392 22max -1(log, , ,,,,，, IR (cm): 2920, 2853 (C-H), 1070 (Ar-O-C). 6