S1 Palladium Catalyzed Bicyclization of 1,8-Diiodonaphthalene and Tertiary Propargylic Alcohols to Phenalenones and Their Applications as Fluorescent Chemosensor for Fluoride Anion Xiaopeng Chen, Hongbo Wang, Xiaohan Jin, Jinwu Feng, Yanguang Wang*, and Ping Lu*a a Chemistry Department, Zhejiang University, 310027, P. R. China Email: pinglu@zju.edu.cn; orgwyg@zju.edu.cn, Fax: (+86) 571-87952543 Supporting Information I. General S2 II. General procedure and Analytical data for all of compounds.S2 III.1 H-NMR and 13 C-NMR Spectra of those compounds.S10 IV.The selectivity of 3a with various anions.S36 V. The color change of 3a with the titration with F- S36 VI. Computational Details of 3a.S37 VII. References.S37 S2 General: Melting points were recorded on a B?CHI 535. NMR spectra were obtained on a Bruker AVANCE DMX500 spectrometer operating at 500 MHz for 1 H-NMR and 125 MHz for 13 C-NMR in CDCl3. All electron impact mass spectra were recorded on Agilent 5973N MSD instrument and all high-resolution mass spectra (HRMS) were recorded on Waters Micromass GCT instrument. UV-vis absorption spectra were recorded on a Shimadzu UV-2450 spectrophotometer. Fluorescence spectra were recorded on a Shimadzu RF-5301PC spectrofluorophotometer. Flash column chromatography was performed employing 300-400 mesh silica gel. Thin layer chromatography (TLC) was performed on silica gel HSGF254. Triethylamine, diisopropylamine, N,N-diisopropylethylamine, pyrrolidine, piperidine, tetrahydrofuran (THF), dichloromethane, ethyl acetate, hexane, 1,8-dibromonaphthalene, tetrabutylammonium fluoride(1M in THF, contain 5%H2O) (acros), tetrabutylammonium chloride (acros), tetrabutylammonium bromide (acros), tetrabutylammonium hydroxide(1M in H2O) (acros), 2-methylbut-3-yn-2-ol (2a) (acros), 3-methylpent-1-yn-3-ol (2b) (acros), 1-ethynylcyclohexanol (2f) (acros), prop-2-yn-1-ol (2k), Pd(PPh3)2Cl2 (acros), Pd(OAc)2 (acros), Pd(PPh3)4 (acros) were used as received. 1,8-Diiodonaphthalene (1), 3-methylhex-1-yn-3-ol (2c), 3-ethylpent-1-yn-3-ol (2d), 1-ethynylcyclopentanol (2e), 3,5-dimethylhex-1-yn-3-ol (2g), hex-1-yn-3-ol (2h), non-1-yn-3-ol (2i), 1-phenylprop-2-yn-1-ol (2j) were synthesized employing published procedures.1,2 1. 1-hydroxy-8,8-dimethyl-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3a): O OH O H3C CH3 O (a) General Procedure for Pd(PPh3)2Cl2/CuI-catalyzed bicyclization of 1,8-diiodonaphthalene (1) and 2-methylbut-3-yn-2-ol (2a): To a solution of 1 (380 mg, 1 mmol) and 2a (336 mg, 4 mmol) in Et3N (40 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) were added at ambient temperature. The reaction mixture is purged with nitrogen for 10 min. Then water (10 ?L) and air (5 mL) was mixed in by syringe and the sealed flask was heated at 80 o C for about 10 h. After complete consumption of starting material as tracked by TLC, Et3N was removed under redeuced pressure and the residue was dissolved with ether, washed with water, and dried over Na2SO4. After filtration, the filtrate was distilled under reduced pressure and the residue was purified via flash chromatography on silica gel (dichloromethane/hexane = 1:2). 3a (179 mg, 64%) was obtained. (b) Under the reaction conditions claimed above, 5a (336 mg, 1 mmol) and 2a (168 mg, 2 mmol) in 20 mL of Et3N also afforded 3a (190 mg) in yield of 68%. S3 3a: orange solid, m.p. 232.8-234.4 o C. Crystal structure of 3a: 1 H-NMR (Figure S1): δ 13.28 (s, 1H), 8.74 (d, J = 7.60 Hz, 1H), 8.18 (d, J = 7.60 Hz, 1H), 8.00 (d, J = 9.10 Hz, 1H), 7.70 (dd, J1 = J2 = 7.60 Hz, 1H), 7.23 (d, J = 9.10 Hz, 1H), 1.87 (s, 6H); 13 C-NMR (Figure S2): δ 25.2, 91.2, 104.5, 122.5, 125.4, 128.7, 130.2, 130.6, 131.9, 132.5, 137.1, 137.6, 152.7, 163.2, 175.5, 178.9; EIMS: m/z 280 (M+ , 41.24), 237 (100); HRMS: cacld. for C17H12O4 [M+ ], 280.0685; found, 280.0695. 2. 8-ethyl-1-hydroxy-8-methyl-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3b): O OH O C2H5 CH3 O (a) The reaction of 1 (380 mg, 1 mmol), 2b (392 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 3b (182 mg ) in yield of 62%. (b) The reaction of 5a (336 mg, 1 mmol), 2b (196 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 mL of Et3N also afforded 3b (191 mg) in yield of 65%. 3b: orange solid, m.p. 165.8-167.2 o C. 1 H-NMR (Figure S3): δ 13.33 (s, 1H), 8.75 (d, J = 7.60 Hz, 1H), 8.20 (d, J = 7.60 Hz, 1H), 8.03 (d, J = 9.00 Hz, 1H), 7.72 (dd, J1 = J2 = 7.60 Hz, 1H), 7.26 (d, J = 9.00 Hz, 1H), 2.31 (q, J = 7.40 Hz, 2H), 1.85 (s, 3H), 0.82 (t, J = 7.40 Hz, 3H); 13 C-NMR (Figure S4): δ 8.2, 24.0, 30.5, 94.0, 104.5, 122.6, 125.4, 128.8, 130.3, 130.5, 132.1, 133.4, 137.1, 137.6, 151.6, 163.2, 175.8, 178.9; EIMS: m/z 294 (M+ , 47.36), 266 (100); HRMS: cacld. for C18H14O4 [M+ ], 294.0892; found, 294.0887. S4 3. 1-hydroxy-8-methyl-8-propyl-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3c): O OH O n-C3H7 CH3 O (a) The reaction of 1 (380 mg, 1 mmol), 2c (448 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 3c (179 mg) in yield of 58%. (b) The reaction of 5a (336 mg, 1 mmol), 2c (224 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 mL of Et3N also afforded 3c (191 mg) in yield of 62%. 3c: orange solid, m.p. 109.5-110.8 o C. 1 H-NMR (Figure S5): δ 13.32 (s, 1H), 8.74 (d, J = 7.50 Hz, 1H), 8.19 (d, J = 7.50 Hz, 1H), 8.01 (d, J = 9.00 Hz, 1H), 7.71 (dd, J1 = J2 = 7.50 Hz, 1H), 7.24 (d, J = 9.00 Hz, 1H), 2.27-2.20 (m, 2H), 1.85 (s, 3H), 1.36-1.30 (m, 1H), 1.14-1.08 (m, 1H), 0.88 (t, J = 7.50 Hz, 1H); 13 C-NMR (Figure S6): δ 14.1, 17.3, 24.2, 39.4, 93.7, 104.5, 122.5, 125.4, 128.7, 130.2, 130.3, 132.0, 133.1, 137.1, 137.6, 151.8, 163.2, 175.7, 178.9; EIMS: m/z 308 (M+ , 12.94), 266 (100); HRMS: cacld. for C19H16O4 [M+ ], 308.1049; found, 308.1053. 4. 8,8-diethyl-1-hydroxy-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3d): O OH O C2H5 C2H5 O (a) The reaction of 1 (380 mg, 1 mmol), 2d (448 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 3d (138 mg) in yield of 45%. (b) The reaction of 5a (336 mg, 1 mmol), 2d (224 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 mL of Et3N also afforded 3d (132 mg) in yield of 43%. S5 3d: orange solid, m.p. 105.8-107.3 o C. 1 H-NMR (Figure S7): δ 13.36 (s, 1H), 8.75 (d, J = 8.00 Hz, 1H), 8.21 (d, J = 8.00 Hz, 1H), 8.04 (d, J = 9.50 Hz, 1H), 7.72 (dd, J1 = J2 = 8.00 Hz, 1H), 7.27 (d, J = 9.50 Hz, 1H), 2.38 (m, 2H), 2.27(m, 2H), 0.78 (t, J = 8.50 Hz, 6H); 13 C-NMR (Figure S8): δ 8.0, 29.6, 97.1, 104.6, 122.6, 125.4, 128.8, 130.2, 130.3, 132.1, 133.6, 137.1, 137.6, 150.0, 163.1, 176.0, 178.8; EIMS: m/z 308 (M+ , 46.29), 280 (100); HRMS: cacld. for C19H16O4 [M+ ], 308.1049; found, 308.1046. 5. 8,8-cyclopentyl-1-hydroxy-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3e): O OH O O (a) The reaction of 1 (380 mg, 1 mmol), 2e (440 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 3e (180 mg) in yield of 59%. (b) The reaction of 5a (336 mg, 1 mmol), 2e (220 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 mL of Et3N also afforded 3e (187 mg) in yield of 61%. 3e: yellow solid, m.p. 166.0-167.1 o C. 1 H-NMR (Figure S9): δ 13.34 (s, 1H), 8.75 (d, J = 7.60 Hz, 1H), 8.20 (d, J = 7.60 Hz, 1H), 8.01 (d, J = 9.00 Hz, 1H), 7.71 (dd, J1 = J2 = 7.60 Hz, 1H), 7.25 (d, J = 9.00 Hz, 1H), 2.72-2.66 (m, 2H), 2.10 (m, 4H),2.00-1.95 (m, 2H); 13 C-NMR (Figure S10): δ 25.4, 39.9, 101.2, 104.6, 122.5, 125.4, 128.7, 130.2, 130.4, 131.9, 133.1, 137.1, 137.5, 149.9, 163.1, 175.6, 179.1; EIMS: m/z 306 (M+ , 43.06), 265 (100); HRMS: cacld. for C19H14O4 [M+ ], 306.0892; found, 306.0898. 6. 8,8-cyclohexyl-1-hydroxy-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3f): O OH O O (a) The reaction of 1 (380 mg, 1 mmol), 2f (496 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in S6 40 ml of Et3N afforded 3f (192 mg) in yield of 60%. (b) The reaction of 5a (336 mg, 1 mmol), 2f (248 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 ml of Et3N also afforded 3f (192 mg) in yield of 60%. 3f : orange solid, m.p. 242.5-243.8 o C. 1 H-NMR (Figure S11): δ 13.40 (s, 1H), 8.73 (d, J = 7.60 Hz, 1H), 8.18 (d, J = 7.60 Hz, 1H), 8.00 (d, J = 9.00 Hz, 1H), 7.70 (dd, J1 = J2 = 7.60 Hz, 1H), 7.24 (d, J = 9.00 Hz, 1H), 2.61-2.54 (m, 2H), 1.89-1.72 (m, 5H),1.70 (m, 2H), 1.46 (m, 1H); 13 C-NMR (Figure S12): δ 22.3, 24.5, 33.6, 93.1, 104.6, 122.6, 125.3, 128.7, 130.1, 130.7, 132.0, 132.6, 137.0, 137.5, 152.8, 163.2, 175.8, 179.0; EIMS: m/z 320 (M+ ,56.32), 265 (100); HRMS: cacld. for C20H16O4 [M+ ], 320.1049; found, 320.1049. 7. 1-hydroxy-8-isobutyl-8-methyl-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3g): O OH O O (a) The reaction of 1 (380 mg, 1 mmol), 2g (504 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 ml of Et3N afforded 3g (174 mg) in yield of 54%. (b) The reaction of 5a (336 mg, 1 mmol), 2g (252 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 ml of Et3N also afforded 3g (182 mg) in yield of 55%. 3g: orange solid, m.p. 274.5-275.8 o C. 1 H-NMR (Figure S13): δ 13.36 (s, 1H), 8.75 (d, J = 7.60 Hz, 1H), 8.20 (d, J = 7.60 Hz, 1H), 8.02 (d, J = 9.00 Hz, 1H), 7.72 (dd, J1 = J2 = 7.60 Hz, 1H), 7.27 (d, J = 9.00 Hz, 1H), 2.23 (dd, J1 = J2 = 5.75 Hz, 2H), 2.16 (dd, J1 = J2 = 6.60 Hz, 2H), 1.84(s, 3H), 1.60 (m, 1H), 0.93 (d, J = 7.15 Hz , 3H), 0.83 (d, J = 7.15 Hz , 3H); 13 C-NMR (Figure S14): δ 24.0, 23.4, 24., 24.8, 45.6, 93.8, 104.5, 122.5, 125.3, 128.7, 130.2, 130.4, 132.1, 133.0, 137.1, 137.6, 152.2, 163.2, 175.8, 179.0; EIMS: m/z 322 (M+ , 2.06), 266 (100); HRMS: cacld. for C20H18O4 [M+ ], 322.1205; found, 322.1206. S7 8. 1-(8-iodonaphthalen-1-yl)hex-1-yn-3-ol (5h): OH n-C3H7 H I The reaction of 1 (380 mg, 1 mmol), 2h (392 mg, 4 mmol), water (10?L), air (5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 5h (262 mg) in yield of 75%. 5h: colorless oil. 1 H-NMR (Figure S15): δ 8.27 (dd, J1 = 7.32 Hz and J2 = 1.20 Hz, 1H), 7.82-7.78 (m, 3H), 7.40 (dd, J1 = J2 = 7.67 Hz, 1H), 7.09 (dd, J1 = J2 = 7.72 Hz, 1H), 4.72 (t, J = 6.58, 1H), 1.99 (br, 1H), 1.91-1.86 (m, 2H), 1.64-1.60 (m, 2H), 1.00 (t, J = 7.45 Hz, 3H); 13 C-NMR (Figure S16): δ 14.1, 18.8, 39.4, 63.8, 84.6, 93.1, 101.8, 122.3, 125.6, 127.3, 130.4, 130.7, 132.1, 135.0, 136.4, 142.9; EIMS: m/z 350 (M+ , 11.82), 152 (100); HRMS: cacld. for C16H15OI [M+ ], 350.0168; found, 350.0166. 9. 1-(8-iodonaphthalen-1-yl)non-1-yn-3-ol (5i): OH n-C6H13 H I The reaction of 1 (380 mg, 1 mmol), 2i (560 mg, 4 mmol), water (10 ?L), air (5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 5i (290 mg) in yield of 74%. 5i: colorless oil. 1 H-NMR (Figure S17): δ 8.25 (dd, J1 = 7.32 Hz and J2 = 1.00 Hz, 1H), 7.80-7.74 (m, 3H), 7.37 (dd, J1 = J2 = 7.67 Hz, 1H), 7.06 (dd, J1 = J2 = 7.70 Hz, 1H), 4.70 (t, J = 6.60 Hz, 1H), 2.17 (br, 1H), 1.92-1.86 (m, 2H), 1.58-1.55 (m, 2H), 1.38-1.29 (m, 6H), 0.88 (t, J = 6.90, 3H); 13 C-NMR (Figure S18): δ 14.3, 22.8, 25.5, 29.3, 32.0, 37.3, 64.0, 84.6, 93.1, 101.9, 122.4, 125.6, 127.3, 130.4, 130.7, 132.1, 135.0, 136.4, 142.9; EIMS: m/z 392 (M+ , 12.29), 152 (100); HRMS: cacld. for C19H21OI [M+ ], 392.0637; found, 392.0638. S8 10. 3-(8-iodonaphthalen-1-yl)-1-phenylprop-2-yn-1-ol (5j): OH H I The reaction of 1 (380 mg, 1 mmol), 2j (528 mg, 4 mmol), water (10 ?L), air (5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol),CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 5j (274 mg) in yield of 72%. 5j: colorless oil. 1 H-NMR (Figure S19): δ 8.25 (dd, J1 = 7.32 Hz and J2 = 0.86 Hz, 1H), 7.86 (d, J = 7.22 Hz, 1H), 7.80 (dd, J1 = J2 = 7.05 Hz, 2H), 7.67 (d, J = 7.46 Hz, 2H), 7.43-7.34 (m, 4H), 5.80 (d, J = 4.80 Hz, 1H), 2.50 (d, J = 5.30, 1H); 13 C-NMR (Figure S20): δ 66.2, 86.4, 93.0, 100.1, 122.1, 125.6, 127.2, 127.4, 128.6,128.9, 130.4, 131.0, 132.2, 135.1, 136.6, 140.3, 142.9; EIMS: m/z 384 (M+ , 50.18), 257 (100); HRMS: cacld. for C19H13OI [M+ ], 380.0011; found, 380.0012. 11. acenaphthylen-1-ylmethanol3 (6): OH The reaction of 1 (380 mg, 1 mmol), 2k (224 mg, 4 mmol), water (10 ?L), air (5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol),CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 6 (138 mg) in yield of 76%. 6: yellow solid, m.p. 52.6-55.5 o C (Lit.3 , 49-50 o C) 1 H-NMR (Figure S21): δ 7.77 (d, J = 8.15 Hz, 1H), 7.73 (d, J = 9.20 Hz, 1H), 7.71 (d, J = 6.75 Hz, 1H), 7.57 (d, J = 6.75 Hz, 1H), 7.51-7.46 (m, 2H), 6.89 (s, 1H), 4.88 (s, 2H), 1.94 (s, 1H); 13 C-NMR (Figure S22): δ 60.1, 123.1, 124.1, 125.9, 127.2, 127.7, 128.0, 128.3, 129.3, 138.6, 139.0, 143.4; EIMS: m/z 181 (M+ , 85.93), 153 (100); HRMS: cacld. for C13H10O [M+ ], 182.0732; found, 182.0732. 12. 4,4'-(naphthalene-1,8-diyl)bis(2-methylbut-3-yn-2-ol)4 (4a): OH OH General Procedure for Pd(PPh3)2Cl2/CuI-catalyzed Sonogashira coupling reaction of S9 1,8-diiodonaphthalene (1) and 2-methylbut-3-yn-2-ol (2a): To a solution of 1 (380 mg, 1 mmol) and 2a (336 mg, 4 mmol) in 40 mL of Et3N, Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) were added at ambient temperature. The reaction mixture is purged with nitrogen for 10 min. Then the sealed flask was heated at 80 o C for about 20 h. After complete consumption of starting material as determined by TLC, Et3N was removed and the residue was dissolved with ether, washed with water, and dried by Na2SO4. After filtration, the filtrate was distilled under reduced pressure and the residue was purified via flash chromatography on silica gel (ethyl acetate/ hexane = 1:4). 4a (276 mg, 94%) was obtained. 4a: white solid, m.p. 119.4-120.6 o C (Lit4 120-121 o C) 1 H-NMR (Figure S23): δ 7.75 (d, J = 8.25 Hz, 2H), 7.66 (d, J = 7.20 Hz, 2H), 7.37 (dd, J1 = J2 = 7.64 Hz, 2H), 4.52 (s, 2H), 1.68 (s, 12H); 13 C-NMR (Figure S24): δ 31.8, 66.1, 82.4, 100.6, 120.7, 125.6, 129.6, 131.2, 134.2, 135.2. 13. 4-(8-iodonaphthalen-1-yl)-2-methylbut-3-yn-2-ol4 (5a): I OH The reaction of 1 (1140 mg, 3 mmol), 2a (168 mg, 2 mmol), Pd(PPh3)2Cl2 (70.2 mg, 0.05 mmol), CuI (38.2 mg, 0.10 mmol) and PPh3 (52.4mg, 0.10 mmol) in 40 mL of Et3N, afforded 5a (618 mg, 92%). 5a: colorless oil. 1 H-NMR (Figure S25): δ 8.26 (d, J=7.35 Hz, 1H), 7.81-7.76 (m, 3H), 7.38 (dd, J1 = J2 = 7.68 Hz, 1H), 7.08 (dd, J1 = J2 = 7.72 Hz, 1H), 2.13 (br, 1H), 1.68 (s, 6H); 13 C-NMR (Figure S26): δ 30.9, 66.1, 81.5, 93.1, 104.6, 122.4, 125.5, 127.1, 130.3, 130.52, 131.9, 134.9, 136.5, 142.6. Figure S1 1 H-NMR spectrum of 3a. S10 S11 Figure S2 13 C-NMR spectrum of 3a. S12 Figure S3 1 H-NMR spectrum of 3b. Figure S4 13 C-NMR spectrum of 3b. S13 Figure S5 1 H-NMR spectrum of 3c. S14 Figure S6 13 C-NMR spectrum of 3c. S15 Figure S7 1 H-NMR spectrum of 3d. S16 Figure S8 13 C-NMR spectrum of 3d. S17 Figure S9 1 H-NMR spectrum of 3e. S18 Figure S10 13 C-NMR spectrum of 3e. S19 Figure S11 1 H-NMR spectrum of 3f. S20 Figure S12 13 C-NMR spectrum of 3f. S21 Figure S13 1 H-NMR spectrum of 3g. S22 Figure S14 13 C-NMR spectrum of 3g. S23 Figure S15 1 H-NMR spectrum of 5h. S24 Figure S16 13 C-NMR spectrum of 5h. S25 Figure S17 1 H-NMR spectrum of 5i. S26 Figure S18 13 C-NMR spectrum of 5i. S27 Figure S19 1 H-NMR spectrum of 5j. S28 Figure S20 13 C-NMR spectrum of 5j. S29 Figure S21 1 H-NMR spectrum of 6. S30 S31 Figure S22 13 C-NMR spectrum of 6. S32 Figure S23 1 H-NMR spectrum of 4a. S33 Figure S24 13 C-NMR spectrum of 4a. S34 Figure S25 1 H-NMR spectrum of 5a. S35 Figure S26 13 C-NMR spectrum of 5a. S36 Figure S27 The Color of 3a (1 * 10-5 M in THF) exposed to daylight before (left, canary yellow) and after (right, orange) titration with F- . Figure S28 The color of 3a (1 * 10-5 M in THF) excited at 454 nm before (left, dark green) and after (right, bright yellow) titration with F- . 500 550 600 650 0 30 60 90 120 150 F- Intensity Wavelength (nm) 465 AcO- Cl- Br- H2PO4 - HPO4 2- 0 1 2 3 4 100 150 200 250 300 relative intensity (I 551 nm / I 480 nm) AcO- F- Cl- Br- H2PO4 - HPO4 2- blank (b) Figure S29 (a) The fluorescent spectra of 3a (1*10-5 M) in THF with various anions. (b) The selectivity of 3a with various anions:Its relative fluorescence intensities (from left to right: blank, AcO- , Cl- , Br- , HPO4 2- , H2PO4 - and F- ). S37 Table S1 the computational orbital energy of naphthalene, phenalenone and 3a (all in eV at B3LYP/6-31G* level) using Gaussian 03 programs.5 compound naphthalene phenalenone 3a sturcture -0.634 e -0.610 e -0.543 e -0.174 e LUMO (eV) -1.11 -2.61 -3.00 HOMO (eV) -5.90 -6.19 -6.00 Eg (eV) 4.79 3.58 3.00 + - Figure S30 Total charge density of 3a References: 1 For the synthesis of 1,8-diiodonaphthalene, see: H. House, D. Koepsell and W. J . Campbell, J. Org. Chem. 1972, 37, 1003. 2 For the synthesis of propynols, see: Z. Lu and S. Ma, J. Org. Chem. 2006, 71, 2655; J. –J. Liu, F. Konzelmann, K. –C. Luk, Tetrahedron Lett. 2003, 44, 3901. 3 N. Haddad and E. A. –Shqara, J. Org. Chem. 1994, 59, 6090. 4 J. J. González, A. Francesch, D. J. Cárdenas and A. M. Echavarren, J. Org. Chem. 1998, 63, 2854. 5 I. V. Alabugin and M. Manoharan, J. Am. Chem. Soc. 2005, 127, 9534.
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S1 Palladium Catalyzed Bicyclization of 1,8-Diiodonaphthalene and Tertiary Propargylic Alcohols to Phenalenones and Their Applications as Fluorescent Chemosensor for Fluoride Anion Xiaopeng Chen, Hongbo Wang, Xiaohan Jin, Jinwu Feng, Yanguang Wang*, and Ping Lu*a a Chemistry Department, Zhejiang University, 310027, P. R. China Email: pinglu@zju.edu.cn; orgwyg@zju.edu.cn, Fax: (+86) 571-87952543 Supporting Information I. General S2 II. General procedure and Analytical data for all of compounds.S2 III.1 H-NMR and 13 C-NMR Spectra of those compounds.S10 IV.The selectivity of 3a with various anions.S36 V. The color change of 3a with the titration with F- S36 VI. Computational Details of 3a.S37 VII. References.S37 S2 General: Melting points were recorded on a B?CHI 535. NMR spectra were obtained on a Bruker AVANCE DMX500 spectrometer operating at 500 MHz for 1 H-NMR and 125 MHz for 13 C-NMR in CDCl3. All electron impact mass spectra were recorded on Agilent 5973N MSD instrument and all high-resolution mass spectra (HRMS) were recorded on Waters Micromass GCT instrument. UV-vis absorption spectra were recorded on a Shimadzu UV-2450 spectrophotometer. Fluorescence spectra were recorded on a Shimadzu RF-5301PC spectrofluorophotometer. Flash column chromatography was performed employing 300-400 mesh silica gel. Thin layer chromatography (TLC) was performed on silica gel HSGF254. Triethylamine, diisopropylamine, N,N-diisopropylethylamine, pyrrolidine, piperidine, tetrahydrofuran (THF), dichloromethane, ethyl acetate, hexane, 1,8-dibromonaphthalene, tetrabutylammonium fluoride(1M in THF, contain 5%H2O) (acros), tetrabutylammonium chloride (acros), tetrabutylammonium bromide (acros), tetrabutylammonium hydroxide(1M in H2O) (acros), 2-methylbut-3-yn-2-ol (2a) (acros), 3-methylpent-1-yn-3-ol (2b) (acros), 1-ethynylcyclohexanol (2f) (acros), prop-2-yn-1-ol (2k), Pd(PPh3)2Cl2 (acros), Pd(OAc)2 (acros), Pd(PPh3)4 (acros) were used as received. 1,8-Diiodonaphthalene (1), 3-methylhex-1-yn-3-ol (2c), 3-ethylpent-1-yn-3-ol (2d), 1-ethynylcyclopentanol (2e), 3,5-dimethylhex-1-yn-3-ol (2g), hex-1-yn-3-ol (2h), non-1-yn-3-ol (2i), 1-phenylprop-2-yn-1-ol (2j) were synthesized employing published procedures.1,2 1. 1-hydroxy-8,8-dimethyl-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3a): O OH O H3C CH3 O (a) General Procedure for Pd(PPh3)2Cl2/CuI-catalyzed bicyclization of 1,8-diiodonaphthalene (1) and 2-methylbut-3-yn-2-ol (2a): To a solution of 1 (380 mg, 1 mmol) and 2a (336 mg, 4 mmol) in Et3N (40 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) were added at ambient temperature. The reaction mixture is purged with nitrogen for 10 min. Then water (10 ?L) and air (5 mL) was mixed in by syringe and the sealed flask was heated at 80 o C for about 10 h. After complete consumption of starting material as tracked by TLC, Et3N was removed under redeuced pressure and the residue was dissolved with ether, washed with water, and dried over Na2SO4. After filtration, the filtrate was distilled under reduced pressure and the residue was purified via flash chromatography on silica gel (dichloromethane/hexane = 1:2). 3a (179 mg, 64%) was obtained. (b) Under the reaction conditions claimed above, 5a (336 mg, 1 mmol) and 2a (168 mg, 2 mmol) in 20 mL of Et3N also afforded 3a (190 mg) in yield of 68%. S3 3a: orange solid, m.p. 232.8-234.4 o C. Crystal structure of 3a: 1 H-NMR (Figure S1): δ 13.28 (s, 1H), 8.74 (d, J = 7.60 Hz, 1H), 8.18 (d, J = 7.60 Hz, 1H), 8.00 (d, J = 9.10 Hz, 1H), 7.70 (dd, J1 = J2 = 7.60 Hz, 1H), 7.23 (d, J = 9.10 Hz, 1H), 1.87 (s, 6H); 13 C-NMR (Figure S2): δ 25.2, 91.2, 104.5, 122.5, 125.4, 128.7, 130.2, 130.6, 131.9, 132.5, 137.1, 137.6, 152.7, 163.2, 175.5, 178.9; EIMS: m/z 280 (M+ , 41.24), 237 (100); HRMS: cacld. for C17H12O4 [M+ ], 280.0685; found, 280.0695. 2. 8-ethyl-1-hydroxy-8-methyl-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3b): O OH O C2H5 CH3 O (a) The reaction of 1 (380 mg, 1 mmol), 2b (392 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 3b (182 mg ) in yield of 62%. (b) The reaction of 5a (336 mg, 1 mmol), 2b (196 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 mL of Et3N also afforded 3b (191 mg) in yield of 65%. 3b: orange solid, m.p. 165.8-167.2 o C. 1 H-NMR (Figure S3): δ 13.33 (s, 1H), 8.75 (d, J = 7.60 Hz, 1H), 8.20 (d, J = 7.60 Hz, 1H), 8.03 (d, J = 9.00 Hz, 1H), 7.72 (dd, J1 = J2 = 7.60 Hz, 1H), 7.26 (d, J = 9.00 Hz, 1H), 2.31 (q, J = 7.40 Hz, 2H), 1.85 (s, 3H), 0.82 (t, J = 7.40 Hz, 3H); 13 C-NMR (Figure S4): δ 8.2, 24.0, 30.5, 94.0, 104.5, 122.6, 125.4, 128.8, 130.3, 130.5, 132.1, 133.4, 137.1, 137.6, 151.6, 163.2, 175.8, 178.9; EIMS: m/z 294 (M+ , 47.36), 266 (100); HRMS: cacld. for C18H14O4 [M+ ], 294.0892; found, 294.0887. S4 3. 1-hydroxy-8-methyl-8-propyl-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3c): O OH O n-C3H7 CH3 O (a) The reaction of 1 (380 mg, 1 mmol), 2c (448 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 3c (179 mg) in yield of 58%. (b) The reaction of 5a (336 mg, 1 mmol), 2c (224 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 mL of Et3N also afforded 3c (191 mg) in yield of 62%. 3c: orange solid, m.p. 109.5-110.8 o C. 1 H-NMR (Figure S5): δ 13.32 (s, 1H), 8.74 (d, J = 7.50 Hz, 1H), 8.19 (d, J = 7.50 Hz, 1H), 8.01 (d, J = 9.00 Hz, 1H), 7.71 (dd, J1 = J2 = 7.50 Hz, 1H), 7.24 (d, J = 9.00 Hz, 1H), 2.27-2.20 (m, 2H), 1.85 (s, 3H), 1.36-1.30 (m, 1H), 1.14-1.08 (m, 1H), 0.88 (t, J = 7.50 Hz, 1H); 13 C-NMR (Figure S6): δ 14.1, 17.3, 24.2, 39.4, 93.7, 104.5, 122.5, 125.4, 128.7, 130.2, 130.3, 132.0, 133.1, 137.1, 137.6, 151.8, 163.2, 175.7, 178.9; EIMS: m/z 308 (M+ , 12.94), 266 (100); HRMS: cacld. for C19H16O4 [M+ ], 308.1049; found, 308.1053. 4. 8,8-diethyl-1-hydroxy-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3d): O OH O C2H5 C2H5 O (a) The reaction of 1 (380 mg, 1 mmol), 2d (448 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 3d (138 mg) in yield of 45%. (b) The reaction of 5a (336 mg, 1 mmol), 2d (224 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 mL of Et3N also afforded 3d (132 mg) in yield of 43%. S5 3d: orange solid, m.p. 105.8-107.3 o C. 1 H-NMR (Figure S7): δ 13.36 (s, 1H), 8.75 (d, J = 8.00 Hz, 1H), 8.21 (d, J = 8.00 Hz, 1H), 8.04 (d, J = 9.50 Hz, 1H), 7.72 (dd, J1 = J2 = 8.00 Hz, 1H), 7.27 (d, J = 9.50 Hz, 1H), 2.38 (m, 2H), 2.27(m, 2H), 0.78 (t, J = 8.50 Hz, 6H); 13 C-NMR (Figure S8): δ 8.0, 29.6, 97.1, 104.6, 122.6, 125.4, 128.8, 130.2, 130.3, 132.1, 133.6, 137.1, 137.6, 150.0, 163.1, 176.0, 178.8; EIMS: m/z 308 (M+ , 46.29), 280 (100); HRMS: cacld. for C19H16O4 [M+ ], 308.1049; found, 308.1046. 5. 8,8-cyclopentyl-1-hydroxy-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3e): O OH O O (a) The reaction of 1 (380 mg, 1 mmol), 2e (440 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 3e (180 mg) in yield of 59%. (b) The reaction of 5a (336 mg, 1 mmol), 2e (220 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 mL of Et3N also afforded 3e (187 mg) in yield of 61%. 3e: yellow solid, m.p. 166.0-167.1 o C. 1 H-NMR (Figure S9): δ 13.34 (s, 1H), 8.75 (d, J = 7.60 Hz, 1H), 8.20 (d, J = 7.60 Hz, 1H), 8.01 (d, J = 9.00 Hz, 1H), 7.71 (dd, J1 = J2 = 7.60 Hz, 1H), 7.25 (d, J = 9.00 Hz, 1H), 2.72-2.66 (m, 2H), 2.10 (m, 4H),2.00-1.95 (m, 2H); 13 C-NMR (Figure S10): δ 25.4, 39.9, 101.2, 104.6, 122.5, 125.4, 128.7, 130.2, 130.4, 131.9, 133.1, 137.1, 137.5, 149.9, 163.1, 175.6, 179.1; EIMS: m/z 306 (M+ , 43.06), 265 (100); HRMS: cacld. for C19H14O4 [M+ ], 306.0892; found, 306.0898. 6. 8,8-cyclohexyl-1-hydroxy-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3f): O OH O O (a) The reaction of 1 (380 mg, 1 mmol), 2f (496 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in S6 40 ml of Et3N afforded 3f (192 mg) in yield of 60%. (b) The reaction of 5a (336 mg, 1 mmol), 2f (248 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 ml of Et3N also afforded 3f (192 mg) in yield of 60%. 3f : orange solid, m.p. 242.5-243.8 o C. 1 H-NMR (Figure S11): δ 13.40 (s, 1H), 8.73 (d, J = 7.60 Hz, 1H), 8.18 (d, J = 7.60 Hz, 1H), 8.00 (d, J = 9.00 Hz, 1H), 7.70 (dd, J1 = J2 = 7.60 Hz, 1H), 7.24 (d, J = 9.00 Hz, 1H), 2.61-2.54 (m, 2H), 1.89-1.72 (m, 5H),1.70 (m, 2H), 1.46 (m, 1H); 13 C-NMR (Figure S12): δ 22.3, 24.5, 33.6, 93.1, 104.6, 122.6, 125.3, 128.7, 130.1, 130.7, 132.0, 132.6, 137.0, 137.5, 152.8, 163.2, 175.8, 179.0; EIMS: m/z 320 (M+ ,56.32), 265 (100); HRMS: cacld. for C20H16O4 [M+ ], 320.1049; found, 320.1049. 7. 1-hydroxy-8-isobutyl-8-methyl-7H-phenaleno[1,2-c]furan-7,10(8H)-dione (3g): O OH O O (a) The reaction of 1 (380 mg, 1 mmol), 2g (504 mg, 4 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 ml of Et3N afforded 3g (174 mg) in yield of 54%. (b) The reaction of 5a (336 mg, 1 mmol), 2g (252 mg, 2 mmol), water (10 ?L), air(5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 20 ml of Et3N also afforded 3g (182 mg) in yield of 55%. 3g: orange solid, m.p. 274.5-275.8 o C. 1 H-NMR (Figure S13): δ 13.36 (s, 1H), 8.75 (d, J = 7.60 Hz, 1H), 8.20 (d, J = 7.60 Hz, 1H), 8.02 (d, J = 9.00 Hz, 1H), 7.72 (dd, J1 = J2 = 7.60 Hz, 1H), 7.27 (d, J = 9.00 Hz, 1H), 2.23 (dd, J1 = J2 = 5.75 Hz, 2H), 2.16 (dd, J1 = J2 = 6.60 Hz, 2H), 1.84(s, 3H), 1.60 (m, 1H), 0.93 (d, J = 7.15 Hz , 3H), 0.83 (d, J = 7.15 Hz , 3H); 13 C-NMR (Figure S14): δ 24.0, 23.4, 24., 24.8, 45.6, 93.8, 104.5, 122.5, 125.3, 128.7, 130.2, 130.4, 132.1, 133.0, 137.1, 137.6, 152.2, 163.2, 175.8, 179.0; EIMS: m/z 322 (M+ , 2.06), 266 (100); HRMS: cacld. for C20H18O4 [M+ ], 322.1205; found, 322.1206. S7 8. 1-(8-iodonaphthalen-1-yl)hex-1-yn-3-ol (5h): OH n-C3H7 H I The reaction of 1 (380 mg, 1 mmol), 2h (392 mg, 4 mmol), water (10?L), air (5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 5h (262 mg) in yield of 75%. 5h: colorless oil. 1 H-NMR (Figure S15): δ 8.27 (dd, J1 = 7.32 Hz and J2 = 1.20 Hz, 1H), 7.82-7.78 (m, 3H), 7.40 (dd, J1 = J2 = 7.67 Hz, 1H), 7.09 (dd, J1 = J2 = 7.72 Hz, 1H), 4.72 (t, J = 6.58, 1H), 1.99 (br, 1H), 1.91-1.86 (m, 2H), 1.64-1.60 (m, 2H), 1.00 (t, J = 7.45 Hz, 3H); 13 C-NMR (Figure S16): δ 14.1, 18.8, 39.4, 63.8, 84.6, 93.1, 101.8, 122.3, 125.6, 127.3, 130.4, 130.7, 132.1, 135.0, 136.4, 142.9; EIMS: m/z 350 (M+ , 11.82), 152 (100); HRMS: cacld. for C16H15OI [M+ ], 350.0168; found, 350.0166. 9. 1-(8-iodonaphthalen-1-yl)non-1-yn-3-ol (5i): OH n-C6H13 H I The reaction of 1 (380 mg, 1 mmol), 2i (560 mg, 4 mmol), water (10 ?L), air (5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 5i (290 mg) in yield of 74%. 5i: colorless oil. 1 H-NMR (Figure S17): δ 8.25 (dd, J1 = 7.32 Hz and J2 = 1.00 Hz, 1H), 7.80-7.74 (m, 3H), 7.37 (dd, J1 = J2 = 7.67 Hz, 1H), 7.06 (dd, J1 = J2 = 7.70 Hz, 1H), 4.70 (t, J = 6.60 Hz, 1H), 2.17 (br, 1H), 1.92-1.86 (m, 2H), 1.58-1.55 (m, 2H), 1.38-1.29 (m, 6H), 0.88 (t, J = 6.90, 3H); 13 C-NMR (Figure S18): δ 14.3, 22.8, 25.5, 29.3, 32.0, 37.3, 64.0, 84.6, 93.1, 101.9, 122.4, 125.6, 127.3, 130.4, 130.7, 132.1, 135.0, 136.4, 142.9; EIMS: m/z 392 (M+ , 12.29), 152 (100); HRMS: cacld. for C19H21OI [M+ ], 392.0637; found, 392.0638. S8 10. 3-(8-iodonaphthalen-1-yl)-1-phenylprop-2-yn-1-ol (5j): OH H I The reaction of 1 (380 mg, 1 mmol), 2j (528 mg, 4 mmol), water (10 ?L), air (5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol),CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 5j (274 mg) in yield of 72%. 5j: colorless oil. 1 H-NMR (Figure S19): δ 8.25 (dd, J1 = 7.32 Hz and J2 = 0.86 Hz, 1H), 7.86 (d, J = 7.22 Hz, 1H), 7.80 (dd, J1 = J2 = 7.05 Hz, 2H), 7.67 (d, J = 7.46 Hz, 2H), 7.43-7.34 (m, 4H), 5.80 (d, J = 4.80 Hz, 1H), 2.50 (d, J = 5.30, 1H); 13 C-NMR (Figure S20): δ 66.2, 86.4, 93.0, 100.1, 122.1, 125.6, 127.2, 127.4, 128.6,128.9, 130.4, 131.0, 132.2, 135.1, 136.6, 140.3, 142.9; EIMS: m/z 384 (M+ , 50.18), 257 (100); HRMS: cacld. for C19H13OI [M+ ], 380.0011; found, 380.0012. 11. acenaphthylen-1-ylmethanol3 (6): OH The reaction of 1 (380 mg, 1 mmol), 2k (224 mg, 4 mmol), water (10 ?L), air (5 mL), Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol),CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) in 40 mL of Et3N afforded 6 (138 mg) in yield of 76%. 6: yellow solid, m.p. 52.6-55.5 o C (Lit.3 , 49-50 o C) 1 H-NMR (Figure S21): δ 7.77 (d, J = 8.15 Hz, 1H), 7.73 (d, J = 9.20 Hz, 1H), 7.71 (d, J = 6.75 Hz, 1H), 7.57 (d, J = 6.75 Hz, 1H), 7.51-7.46 (m, 2H), 6.89 (s, 1H), 4.88 (s, 2H), 1.94 (s, 1H); 13 C-NMR (Figure S22): δ 60.1, 123.1, 124.1, 125.9, 127.2, 127.7, 128.0, 128.3, 129.3, 138.6, 139.0, 143.4; EIMS: m/z 181 (M+ , 85.93), 153 (100); HRMS: cacld. for C13H10O [M+ ], 182.0732; found, 182.0732. 12. 4,4'-(naphthalene-1,8-diyl)bis(2-methylbut-3-yn-2-ol)4 (4a): OH OH General Procedure for Pd(PPh3)2Cl2/CuI-catalyzed Sonogashira coupling reaction of S9 1,8-diiodonaphthalene (1) and 2-methylbut-3-yn-2-ol (2a): To a solution of 1 (380 mg, 1 mmol) and 2a (336 mg, 4 mmol) in 40 mL of Et3N, Pd(PPh3)2Cl2 (35.1 mg, 0.05 mmol), CuI (19.1 mg, 0.10 mmol) and PPh3 (26.2 mg, 0.10 mmol) were added at ambient temperature. The reaction mixture is purged with nitrogen for 10 min. Then the sealed flask was heated at 80 o C for about 20 h. After complete consumption of starting material as determined by TLC, Et3N was removed and the residue was dissolved with ether, washed with water, and dried by Na2SO4. After filtration, the filtrate was distilled under reduced pressure and the residue was purified via flash chromatography on silica gel (ethyl acetate/ hexane = 1:4). 4a (276 mg, 94%) was obtained. 4a: white solid, m.p. 119.4-120.6 o C (Lit4 120-121 o C) 1 H-NMR (Figure S23): δ 7.75 (d, J = 8.25 Hz, 2H), 7.66 (d, J = 7.20 Hz, 2H), 7.37 (dd, J1 = J2 = 7.64 Hz, 2H), 4.52 (s, 2H), 1.68 (s, 12H); 13 C-NMR (Figure S24): δ 31.8, 66.1, 82.4, 100.6, 120.7, 125.6, 129.6, 131.2, 134.2, 135.2. 13. 4-(8-iodonaphthalen-1-yl)-2-methylbut-3-yn-2-ol4 (5a): I OH The reaction of 1 (1140 mg, 3 mmol), 2a (168 mg, 2 mmol), Pd(PPh3)2Cl2 (70.2 mg, 0.05 mmol), CuI (38.2 mg, 0.10 mmol) and PPh3 (52.4mg, 0.10 mmol) in 40 mL of Et3N, afforded 5a (618 mg, 92%). 5a: colorless oil. 1 H-NMR (Figure S25): δ 8.26 (d, J=7.35 Hz, 1H), 7.81-7.76 (m, 3H), 7.38 (dd, J1 = J2 = 7.68 Hz, 1H), 7.08 (dd, J1 = J2 = 7.72 Hz, 1H), 2.13 (br, 1H), 1.68 (s, 6H); 13 C-NMR (Figure S26): δ 30.9, 66.1, 81.5, 93.1, 104.6, 122.4, 125.5, 127.1, 130.3, 130.52, 131.9, 134.9, 136.5, 142.6. Figure S1 1 H-NMR spectrum of 3a. S10 S11 Figure S2 13 C-NMR spectrum of 3a. S12 Figure S3 1 H-NMR spectrum of 3b. Figure S4 13 C-NMR spectrum of 3b. S13 Figure S5 1 H-NMR spectrum of 3c. S14 Figure S6 13 C-NMR spectrum of 3c. S15 Figure S7 1 H-NMR spectrum of 3d. S16 Figure S8 13 C-NMR spectrum of 3d. S17 Figure S9 1 H-NMR spectrum of 3e. S18 Figure S10 13 C-NMR spectrum of 3e. S19 Figure S11 1 H-NMR spectrum of 3f. S20 Figure S12 13 C-NMR spectrum of 3f. S21 Figure S13 1 H-NMR spectrum of 3g. S22 Figure S14 13 C-NMR spectrum of 3g. S23 Figure S15 1 H-NMR spectrum of 5h. S24 Figure S16 13 C-NMR spectrum of 5h. S25 Figure S17 1 H-NMR spectrum of 5i. S26 Figure S18 13 C-NMR spectrum of 5i. S27 Figure S19 1 H-NMR spectrum of 5j. S28 Figure S20 13 C-NMR spectrum of 5j. S29 Figure S21 1 H-NMR spectrum of 6. S30 S31 Figure S22 13 C-NMR spectrum of 6. S32 Figure S23 1 H-NMR spectrum of 4a. S33 Figure S24 13 C-NMR spectrum of 4a. S34 Figure S25 1 H-NMR spectrum of 5a. S35 Figure S26 13 C-NMR spectrum of 5a. S36 Figure S27 The Color of 3a (1 * 10-5 M in THF) exposed to daylight before (left, canary yellow) and after (right, orange) titration with F- . Figure S28 The color of 3a (1 * 10-5 M in THF) excited at 454 nm before (left, dark green) and after (right, bright yellow) titration with F- . 500 550 600 650 0 30 60 90 120 150 F- Intensity Wavelength (nm) 465 AcO- Cl- Br- H2PO4 - HPO4 2- 0 1 2 3 4 100 150 200 250 300 relative intensity (I 551 nm / I 480 nm) AcO- F- Cl- Br- H2PO4 - HPO4 2- blank (b) Figure S29 (a) The fluorescent spectra of 3a (1*10-5 M) in THF with various anions. (b) The selectivity of 3a with various anions:Its relative fluorescence intensities (from left to right: blank, AcO- , Cl- , Br- , HPO4 2- , H2PO4 - and F- ). S37 Table S1 the computational orbital energy of naphthalene, phenalenone and 3a (all in eV at B3LYP/6-31G* level) using Gaussian 03 programs.5 compound naphthalene phenalenone 3a sturcture -0.634 e -0.610 e -0.543 e -0.174 e LUMO (eV) -1.11 -2.61 -3.00 HOMO (eV) -5.90 -6.19 -6.00 Eg (eV) 4.79 3.58 3.00 + - Figure S30 Total charge density of 3a References: 1 For the synthesis of 1,8-diiodonaphthalene, see: H. House, D. Koepsell and W. J . Campbell, J. Org. Chem. 1972, 37, 1003. 2 For the synthesis of propynols, see: Z. Lu and S. Ma, J. Org. Chem. 2006, 71, 2655; J. –J. Liu, F. Konzelmann, K. –C. Luk, Tetrahedron Lett. 2003, 44, 3901. 3 N. Haddad and E. A. –Shqara, J. Org. Chem. 1994, 59, 6090. 4 J. J. González, A. Francesch, D. J. Cárdenas and A. M. Echavarren, J. Org. Chem. 1998, 63, 2854. 5 I. V. Alabugin and M. Manoharan, J. Am. Chem. Soc. 2005, 127, 9534.