Supporting Information

S1 Supporting Information Benzannulation from Alkyne without tallic Catalysts at Room Temperature to 100 o C Tienan Jin,* Fan Yang and Yoshinori Yamamoto* Department of Chemistry, Graduate School of Science, Tohoku University Sendai 980-8578, Japan; tjin@mail.tains.tohoku.ac.jp; yoshi@mail.tains.tohoku.ac.jp R 1 MS 4A R 1 O + R 2 H RT or heat R 2 -H 1 2 2 O 3 R 2 R 2 Content: General Information 02 Materials 02 References 02 General Procedure 02 Analytical Data 03 MR Spectra 14

S2 General Information. 1 H MR and 13 C MR spectra were recorded on JEOL JMTC-270/54/SS (JASTEC, 300 MHz, 400 MHz, 500 MHz) spectrometers. 1 H MR spectra are reported as follows: chemical shift in ppm (δ) relative to the chemical shift of CDCl3 at 7.26 ppm, integration, multiplicities (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet and br = broadened), and coupling constants (Hz). 13 C MR spectra reported in ppm (δ) relative to the central line of triplet for CDCl3 at 77 ppm. IR spectra were recorted on JASCO FT/IR-4100 spectrometer; absorptions are reported in cm -1. lting points were measured by MRK (o. 8026). High-resolution mass spectra were obtained on a BRUKER APEXIII spectrometer. Column chromatography was carried out employing Slica gel 60 (spherical, neutral, 40~100 µm, KATO Chemical Co.). Analytical thin-layer chromatography (TLC) was performed on 0.2 mm precoated plate Kieselgel 60 F254 (rk). Materials. All the used anhydrous solvents and various dialkylamines 2 were purchased and used as received. The starting materials, 2-(2-alkynyl)(oxo)benzenes 1, were prepared according to the reported literatures. 1, 2 The structure of products were determined by 1 H-MR, 13 C-MR, OE experiments (3t-v, 4w-x), and reported literatures (3b 3, 3g 4, 3h and 3i 5, 3p 6, 3r 7 ). References es 1. Chang, S., Lee, M.; Jung, D. Y.; Yoo, E. J.; Cho, S. H.; Han, S. K. J. Am. Chem. Soc. 2006, 128, 12366. 2. Knobloch, K.; Keller, M.; Eberbach, W. Eur. J. Org. Chem. 2001, 3313. 3. Cañete, A.; léndrez, M. X.; Saitz, C.; Zanocco, A. L. Synth. Commun. 2001,31, 2143. 4. Ishikawa, T.; Uedo, E.; Tani, R.; Saito, S. J Org. Chem. 2001, 66, 186. 5. Gao, C.-Y.; Yang, L.-M. J Org. Chem. 2008, 73, 1624. 6. Ramana, M. M. V.; Potnis, P. Synthesis 1996, 9, 1090. 7. Gou, F.-R.; Huo, P.-F.; Bi, H.-P.; Guan, Z.-H.; Liang, Y.-M. Org. Lett. 2009, 11, 3418. General procedure Typical procedure for the formation of diethyl-naphthalen naphthalen-2yl 2yl-amine (3a 3a). To a mixture of 2-(prop-2-nyl)benzaldehyde 1a (57.6 mg, 0.4 mmol) and 4Å molecular sieves (200 mg) in 5 ml 2-neck flask equipped with dry tube was added 2 ml of diethylamine. The reaction mixture was stirred at ambient temperature for 2 hours. After consumption of 1a which was monitored by TLC, diethylamine was recovered through distillation. The residue was diluted with dichloromethane, and molecular sieves 4Å was removed by filtration. After concentration, the residue was purified by a short silica gel column (hexane/ethyl acetate = 40/1) to afford 74 mg (93%) of diethyl-naphthalen-2-yl-amine 3a as a colorless oil.

S3 Analytical data 2-(P (Prop rop-2ynyl) 2ynyl)-be benzaldehyde (1a) 1 1a CHO Pale yellow solid; m.p. 39 o C; 1 H MR (400 MHz, CDCl3) δ 10.19 (s, 1H), 7.81 (d, J = 7.6 Hz, 1H), 7.73 (d, J = 7.6 Hz, 1H), 7.59 (dd, J = 7.6, 7.6 Hz, 1H), 7.47 (dd, J = 7.6, 7.6 Hz, 1H), 4.08 (d, J = 2.4 Hz, 2H), 2.25 (t, J = 2.4 Hz, 1H); 13 C MR (100 MHz, CDCl3) δ 22.59, 71.71, 81.10, 127.38, 129.80, 133.13, 133.90, 133.97, 137.87, 192.76; IR(neat): 649, 753, 853, 1197, 1294, 1576, 1601, 1690, 2311 cm -1 ; HRMS (ESI): [M+a] + calcd for C10H8O, 167.0467; found, 167.0467. 4,5-Dimethoxy Dimethoxy-2-(prop (prop-2ynyl) 2ynyl)-benzaldehyde (1b) CHO 1b white solid; m.p. 108-109 o C; 1 H MR (400 MHz, CDCl3) δ 10.17 (s, 1H), 7.34 (s, 1H), 7.17 (s, 1H), 4.04 (d, J = 3.2 Hz, 2H), 4.00 (s, 3H), 3.95 (s, H), 2.27 (t, J = 2.8 Hz, 1H); 13 C MR (75.45 MHz, CDCl3) δ 21.50, 55.89, 55.93, 71.64, 81.20, 112.02, 113.42, 125.88, 132.81, 147.74, 153.43, 189.96; IR(neat): 702, 790, 858, 1103, 1177, 1264, 1519, 1569, 1680, 2314 cm -1 ; HRMS (ESI): [M+a] + calcd for C12H12O3, 227.0679; found, 227.0679. 5-Fluoro Fluoro-2-(prop (prop-2ynyl) 2ynyl)-benzaldehyde (1c) F CHO 1c white solid; m.p. 61.5-62.5 o C; 1 H MR (400 MHz, CDCl3) δ 10.16 (s, 1H), 7.66 (dd, J = 8.8, 4.8 Hz, 1H), 7.49 (dd, J = 8.4, 2.8 Hz, 1H), 7.49 (m. 1H), 3.98 (d, J = 2.4 Hz, 2H), 2.24 (t, J = 2.8 Hz, 1H); 13 C MR (75.45 MHz, CDCl3) δ 21.8, 71.9, 80.8, 118.9 (d, J 3 = 22.2 Hz), 120.8 (d, J 2 = 21.5 Hz), 131.7 (d, J 4 = 6.6 Hz), 133.7 (d, J 6 = 3.3 Hz), 134.5 (d, J 5 = 5.7 Hz), 161.8 (d, J 1 = 247 Hz), 190.8; IR(neat): 658, 684, 778, 1243, 1495, 1586, 1697, 2321 cm -1 ; HRMS (ESI): [M+a] + calcd for C10H7FO, 185.0373; found, 185.0373. 1-Prop Prop-2-ynyl ynyl-naphthalene naphthalene-2-carbaldehyde (1d)

S4 CHO 1d white solid; m.p. 82 o C; 1 H MR (300 MHz, CDCl3) δ 10.58 (s, 1H), 8.34-8.31 (m, 1H), 7.91-7.83 (m, 3H), 7.66-7.61 (m, 2H), 4.42 (d, J = 2.7 Hz, 2H), 2.14 (t, J = 2.7 Hz, 1H); 13 C MR (75.45 MHz, CDCl3) δ 16.33, 70.54, 81.25, 125.14, 125.16, 127.32, 128.29, 128.74, 128.76, 130.41, 131.47, 136.12, 137.29, 191.76; IR(neat): 676, 762, 816, 1226, 1342, 1598, 1619, 1677, 2321 cm -1 ; HRMS (ESI): [M+a] + calcd for C14H10O, 217.0624; found, 217.0623. 1-(2 (2-Prop Prop-2-ynyl ynyl-phenyl) phenyl)-ethanone ethanone (1e) O 1e Yellow oil; 1 H MR (300 MHz, CDCl3) δ 7.76-7.70 (m, 2H), 7.52-7.46 (m, 1H), 7.38-7.32 (m, 1H), 3.96 (d, J = 2.4 Hz, 2H), 2.60 (s, 3H), 2.19 (t, J = 3.0 Hz, 1H); 13 C MR (125 MHz, CDCl3) δ 23.56, 29.32, 70.93, 82.00, 126.78, 129.64, 130.10, 132.05, 136.29, 136.37, 201.31; IR(neat): 759, 958, 1250, 1356, 1573, 1680, 2318 cm -1 ; HRMS (ESI): [M+a] + calcd for C11H10O, 181.0624; found, 181.0623. Phenyl-(2 (2-prop prop-2-ynyl ynyl-phenyl) phenyl)-methanone (1f) O 1f Ph Yellow oil; 1 H MR (400 MHz, CDCl3) δ 7.76-7.74 (m, 2H), 7.64 (d, J = 3.6 Hz, 1H), 7.55-7.51 (m, 1H), 7.46-7.38 (m, 3H), 7.30-7.24 (m, 2H), 3.69 (d, J = 2.4 Hz, 2H), 2.05 (t, J = 2.8 Hz, 1H); 13 C MR (100 MHz, CDCl3) δ 22.70, 70.90, 81.56, 126.15, 128.35, 129.13, 129.46, 130.15, 130.78, 133.16, 135.48, 137.40, 13747, 197.77; IR(neat): 699, 764, 930, 1268, 1315, 1596, 1659, 2318 cm -1 ; HRMS (ESI): [M+a] + calcd for C16H12O, 243.0780; found, 243.0779. 1-(4,5 (4,5-Dimethoxy Dimethoxy-2-prop prop-2-ynyl ynyl-phenyl) phenyl)-ethanone ethanone (1g) 1g O

S5 White solid; m.p. 88-89 o C; 1 H MR (400 MHz, CDCl3) δ 7.19 (s, 1H), 7.18 (s, 1H), 3.89-3.88 (m, 5H), 3.84 (s, 3H), 2.49 (s, 3H), 2.19 (t, J = 3.2 Hz, 1H); 13 C MR (100 MHz, CDCl3) δ 23.32, 28.85, 55.68, 55.96, 70.93, 82.10, 112.55, 113.38, 127.80, 131.02, 146.59, 151.73, 198.80; IR(neat): 739, 857, 1142, 1266, 1511, 1570, 1659, 2314, 3253 cm -1 ; HRMS (ESI): [M+a] + calcd for C13H14O3, 241.0835; found, 241.0834. 1-(5 (5-Chloro Chloro-2-prop prop-2-ynyl ynyl-phenyl) phenyl)-ethanone ethanone (1h) Cl 1h O white solid; m.p. 67-68 o C; 1 H MR (400 MHz, CDCl3) δ 7.68 (d, J = 2.4 Hz, 1H), 7.66 (d, J = 8.4 Hz, 1H), 7.45 (dd, J = 8.4, 2.0 Hz, 1H), 3.88 (d, J = 3.2 Hz, 2H), 3.14 (s, 3H), 2.20 (t, J = 2.8 Hz, 1H); 13 C MR (100 MHz, CDCl3) δ 23.05, 29.26, 71.39, 81.38, 129.43, 131.54, 131.80, 132.62, 134.70, 137.66, 199.92; IR(neat): 679, 806, 837, 894, 1241, 1279, 1479, 1561, 1676, 2317, 2924, 3057 cm -1 ; HRMS (ESI): [M+a] + calcd for C11H9ClO, 215.0234; found, 215.0233. 4-Prop Prop-2-ynyl ynyl-benzaldehyde (1i) OHC 1i Yellow oil; 1 H MR (400 MHz, CDCl3) δ 9.98 (s, 1H), 7.83 (d, J = 8.8 Hz, 2H), 7.53 (d, J = 7.6 Hz, 2H), 3.68 (bs, 2H), 2.27 (bs, 1H); 13 C MR (100 MHz, CDCl3) δ 24.90, 71.38, 80.48, 128.42, 129.89, 135.09, 143.00, 191.67; IR(neat): 774, 804, 1168, 1210, 1306, 1578, 1605, 1690, 2282 cm -1 ; HRMS (EI m/z): [M] + calcd for C10H8O, 144.1; found, 144.1. Diethyl-naphthalen naphthalen-2-yl yl-amine (3a) Et 2 3a Colorless oil; 1 H MR (500 MHz, CDCl3) δ 7.76-7.75 (m, 2H), 7.71 (d, J = 8.0 Hz, 1H), 7.45-7.42 (m, 1H), 7.27-7.24 (m, 1H), 7.20 (dd, J = 9.0, 2.5 Hz, 1H), 6.98 (d, J = 3.0 Hz, 1H), 3.55 (q, J = 7.0 Hz, 4H), 1.31 (t, J = 7.0 Hz, 6H); 13 C MR (100 MHz, CDCl3) δ 12.64, 44.50, 105.51, 115.98, 121.46, 125.83, 126.05, 126.26, 127.34, 128.79, 135.26, 145.78; IR(neat): 740, 801, 820, 1012, 1075, 1357, 1508, 1597, 1626, 2967cm -1 ; HRMS (ESI): [M+H] + calcd for C14H17, 200.1434; found, 200.1432. Dimethyl-naphthalen naphthalen-2-yl yl-amine (3b) 3

S6 2 3b Yellow solid; m.p. 50 o C (lit. 3 50-51 o C); 1 H MR (500 MHz, CDCl3) δ 7.76-7.73 (m, 2H), 7.71 (d, J = 9.0 Hz, 1H), 7.43-7.40 (m, 1H), 7.28-7.24 (m, 1H), 7.22 (dd, J = 9.0, 2.5 Hz, 1H), 6.98 (d, J = 2.5 Hz, 1H), 3.09 (s, 6H); 13 C MR (100 MHz, CDCl3) δ 40.90, 106.51, 108.80, 116.44, 122.05, 126.16, 126.83, 127.40, 128.64, 134.92, 148.61; IR(neat): 740, 802, 824, 965, 1146, 1242, 1509, 1596, 1625, 2800, 3048 cm -1 ; HRMS (ESI): [M+H] + calcd for C12H13, 172.1121; found, 172.1121. Dibutyl-naphthalen naphthalen-2-yl yl-amine (3c) 3c Colorless oil; 1 H MR (300 MHz, CDCl3) δ 7.71 (m, 3H), 7.38-7.33 (m, 1H), 7.20-7.15 (m, 1H), 7.11 (dd, J = 9.0, 2.7 Hz, 1H), 6.87 (d, J = 2.4 Hz, 1H), 3.40 (t, J = 7.5 Hz, 4H), 1.71-1,61 (m, 4H), 1.49-1.36 (m, 4H), 1.01 (t, J = 7.5 Hz, 6H); 13 C MR (75 MHz, CDCl3) δ 14.03, 20.38, 29.52, 50.91, 105.26, 115.90, 121.35, 125.82, 126.04, 126.11, 127.33, 128.70, 135.24, 146.19; IR(neat): 740, 821, 1367, 1509, 1598, 1627, 2871, 2955 cm -1 ; HRMS (ESI): [M+H] + calcd for C18H25, 256.2060; found, 256.2058. (2-thoxy thoxy-ethyl) ethyl)-methyl methyl-naphthalen naphthalen-2-yl yl-amine (3d) O 3d Colorless oil; 1 H MR (300 MHz, CDCl3) δ 7.73-7.65 (m, 3H), 7.40-7.35 (m, 1H), 7.26-7.15 (m, 2H), 6.94 (d, J = 2.7 Hz, 1H), 3.64-3.62 (m, 4H), 3.39 (s, 3H), 3.06 (s, 3H); 13 C MR (75 MHz, CDCl3) δ 39.14, 52.66, 59.04, 70.31, 106.04, 116.05, 121.91, 126.06, 126.16, 126.70, 127.38, 128.74, 135.02, 147.26; IR(neat): 743, 822, 1109, 1509, 1599, 1626, 2875 cm -1 ; HRMS (ESI): [M+H] + calcd for C14H17O, 216.1383; found, 216.1381. thyl-naphthalen naphthalen-2-yl yl-prop prop-2-ynyl ynyl-amine (3e)

S7 3e Colorless oil; 1 H MR (400 MHz, CDCl3) δ 7.77-7.71 (m, 3H), 7.43-7.39 (m, 1H), 7.30-7.23 (m, 2H), 7.12 (d, J = 2.0 Hz, 1H), 4.18 (d, J = 2.8 Hz, 2H), 3.09 (s, 3H), 2.21 (dd, J = 2.8 Hz, 1H); 13 C MR (100 MHz, CDCl3) δ 38.75, 42.81, 72.21, 79.17, 108.98, 117.32, 122.83, 126.24, 126.51, 127.40, 127.71, 128.79, 134.66, 146.89; IR(neat): 744, 803, 827, 1101, 1509, 1599, 1627, 2309, 3055 cm -1 ; HRMS (ESI): [M+H] + calcd for C14H13, 196.1121; found, 196.1120. Allyl-methyl methyl-naphthalen naphthalen-2-yl yl-amine (3f) 3f Colorless oil; 1 H MR (300 MHz, CDCl3) δ 7.76-7.69 (m, 3H), 7.45-7.39 (m, 1H), 7.28-7.23 (m, 1H), 7.19 (dd, J = 9.0, 2.7 Hz, 1H), 6.99 (d, J = 2.7 Hz, 1H), 5.95 (ddt, J = 16.8, 10.5, 5.1 Hz, 1H), 5.29-5.21 (m, 2H), 4.08 (dt, J = 5.1, 1.5 Hz, 2H), 3.09 (s, 3H); 13 C MR (75 MHz, CDCl3) δ 38.22, 55.43, 106.24, 116.22, 116.34, 121.92, 126.07, 126.15, 126.74, 127.39, 128.70, 133.73, 134.99, 147.43; IR(neat): 742, 801, 822, 1187, 1388, 1509, 1599, 1626, 3056 cm -1 ; HRMS (ESI): [M+H] + calcd for C14H15, 198.1277; found, 198.1275. 1-aphthalen aphthalen-2-yl yl-pyrro pyrrolidine (3g) 4 3g White solid; m.p. 92-93 o C (lit. 4 91-91.5 o C); 1 H MR (300 MHz, CDCl3) δ 7.74-7.66 (m, 3H), 7.41-7.36 (m, 1H), 7.26-7.17 (m, 1H), 7.03 (dd, J = 9.0, 2.7 Hz, 1H), 6.80 (d, J = 2.4 Hz, 1H), 3.45-3.41 (m, 4H), 2.10-2.05 (m, 4H); 13 C MR (75 MHz, CDCl3) δ 25.44, 47.76, 104.65, 115.66, 121.13, 125.72, 126.09, 126.25, 127.56, 128.74, 135.24, 145.87; IR(neat): 736, 807, 823, 1147, 1391, 1511, 1596, 1623, 2959 cm -1 ; HRMS (ESI): [M+H] + calcd for C14H15, 198.1277; found, 198.1276. 1-aphthalen aphthalen-2-yl yl-piperidine (3h) 5

S8 3h White solid; m.p. 57-58 o C (lit. 5 56-58 o C); 1 H MR (500 MHz, CDCl3) δ 7.70-7.66 (m, 3H), 7.37 (dd, J = 7.5, 7.7 Hz, 1H), 7.28-7.23 (m, 2H), 7.12 (d, J = 2.5 Hz, 1H), 3.24 (t, J = 5.5 Hz, 4H), 1.78-1.72 (m, 4H), 1.63-1.58 (m, 2H); 13 C MR (125 MHz, CDCl3) δ 24.35, 25.87, 50.99, 110.32, 120.17, 123.06, 126.05, 126.63, 127.34, 128.28, 128.46, 134.68, 150.08; IR(neat): 748, 809, 820, 842, 1114, 1504, 1596, 1626, 2805, 2933 cm -1 ; HRMS (ESI): [M+H] + calcd for C15H17, 212.1434; found, 212.1432. 4-aphthalen aphthalen-2-yl yl-morpholine (3i) 5 O 3i White solid; m.p.87 o C (lit. 5 87-88 o C); 1 H MR (300 MHz, CDCl3) δ 7.77-7.70 (m, 3H), 7.45-7.39 (m, 1H), 7.34-7.24 (m, 2H), 7.13 (d, J = 2.4 Hz, 1H), 3.94-3.91 (m, 4H), 3.28-3.25 (m, 4H); 13 C MR (75 MHz, CDCl3) δ 49.77, 66.92, 110.06, 118.06, 123.51, 126.32, 126.74, 127.41, 128.64, 128.79, 134.50, 149.07; IR(neat): 745, 810, 838, 1117, 1507, 1594, 1625, 1698, 2836 cm -1 ; HRMS (ESI): [M+H] + calcd for C14H15O, 214.1226; found, 214.1225. 4-aphthalen aphthalen-2-yl yl-thiomorpholine (3j) S 3j White solid; m.p. 81-82 o C; 1 H MR (400 MHz, CDCl3) δ 7.78-7.72 (m, 3H), 7.48-7.44 (m, 1H), 7.37-7.33 (m, 1H), 7.25 (dd, J = 9.2, 2.4 Hz, 1H), 7.16 (d, J = 2.4 Hz, 1H), 3.72-3.64 (m, 4H), 2.86-2.83 (m, 4H); 13 C MR (100 MHz, CDCl3) δ 26.93, 52.31, 111.23, 120.15, 123.47, 126.28, 126.64, 127.38, 128.45, 128.85, 134.54, 149.09; IR(neat): 747, 815, 847, 1185, 1505, 1595, 1625, 2309, 2810, 2900 cm -1 ; HRMS (ESI): [M+H] + calcd for C14H15S, 230.0998; found, 230.0997. 1-thyl thyl-4-naphthalen naphthalen-2-yl yl-piperazine (3k)

S9 3k White solid; m.p. 90-92 o C; Isolated by basic alumina column; 1 H MR (300 MHz, CDCl3) δ 7.74-7.67 (m, 3H), 7.42-7.36 (m, 1H), 7.31-7.26 (m, 2H), 7.13 (d, J = 2.4 Hz, 1H), 3.32 (bt, J = 5.1 Hz, 4H), 2.63 (bt, J = 5.1 Hz, 4H), 2.38 (s, 3H); 13 C MR (75 MHz, CDCl3) δ 46.10, 49.42, 55.07, 110.18, 119.31, 123.30, 126.19, 126.67, 127.36, 128.44, 128.61, 134.54, 149.05; IR(neat): 743, 825, 1144, 1221, 1379, 1449, 1596, 1621, 2824, 2943 cm -1 ; HRMS (ESI): [M+H] + calcd for C16H17, 227.1543; found, 227.1542. (6,7-Dimethoxy Dimethoxy-naphthalen naphthalen-2-yl) yl)-diethyl diethyl-amine (3l) Et 2 3l White solid; m.p. 85.5 o C; 1 H MR (500 MHz, CDCl3) δ 7.54 (d, J = 8.8 Hz, 1H), 7.00 (s, 1H), 6.97 (dd, J = 9.3, 2.4 Hz, 1H), 6.96 (s, 1H), 6.82 (d, J = 2.0 Hz, 1H), 3.98 (s, 3H), 3.95 (s, 3H), 3.43 (q, J = 7.2 Hz, 4H), 1.20 (t, J = 7.2 Hz, 6H); 13 C MR (100 MHz, CDCl3) δ 12.63, 44.60, 55.68, 55.77, 104.98, 105.69, 106.37, 114.24, 121.32, 127.23, 130.89, 145.02, 146.54, 149.75; IR(neat): 751, 797, 851, 1131, 1248, 1409, 1514, 1606, 1632, 2964 cm -1 ; HRMS (ESI): [M+H] + calcd for C16H21O2, 260.1645; found, 260.1646. 1-(6,7 (6,7-Dimethoxy Dimethoxy-naphthalen naphthalen-2-yl) yl)-pyrrolidin pyrrolidine (3m) 3m White solid; m.p. 158 o C; 1 H MR (300 MHz, CDCl3) δ 7.55 (d, J = 8.7 Hz, 1H), 7.01 (s, 1H), 6.98 (s, 1H), 6.85 (dd, J = 9.0, 2.0 Hz, 1H), 6.70 (d, J = 2.0 Hz, 1H), 3.98 (s, 3H), 3.96 (s, 3H), 3.39-3.35 (m, 4H), 2.06-2.02 (m, 4H); 13 C MR (100 MHz, CDCl3) δ 25.37, 47.79, 55.61, 55.68, 104.35, 104.72, 106.47, 113.46, 121.10, 127.13, 130.86, 145.08, 146.16, 149.75; IR(neat): 787, 857, 1007, 1131, 1165, 1251, 1424, 1515, 1608, 1628, 2815 cm -1 ; HRMS (ESI): [M+H] + calcd for C16H19O2, 258.1489; found, 258.1490. Diethyl-(6 (6-fluoro fluoro-naphthalen naphthalen-2-yl) yl)-amine (3n)

S10 Et 2 F 3n Yellow oil; 1 H MR (400 MHz, CDCl3) δ 7.60-7.54 (m, 2H), 7.27 (dd, J = 9.6, 2.4 Hz, 1H), 7.14-7.10 (m, 2H), 6.86 (d, J = 2.4 Hz, 1H), 3.42 (q, J = 6.8 Hz, 4H), 1.19 (t, J = 6.8 Hz, 6H); 13 C MR (100 MHz, CDCl3) δ 12.59, 44.51, 105.79, 110.29 (d, J 2 = 20.7 Hz), 116.18 (d, J 3 = 25 Hz), 117.18, 126.28 (d, J 4 = 8.2 Hz), 127.84 (d, J 5 = 8.3 Hz), 128.03 (d, J 6 = 4.9), 132.22, 145.34 (d, J 7 = 2.4 Hz), 158.24 (d, J 1 = 239 Hz); IR(neat): 739, 790, 841, 867, 1109, 1188, 1237, 1506, 1569, 1606, 2930, 2977 cm -1 ; HRMS (ESI): [M+H] + calcd for C14H16F, 218.1340; found, 218.1338. 1-(6 (6-Fluoro Fluoro-naphthalen naphthalen-2-yl) yl)-pyrrolidine (3o) F 3o White solid; m.p. 145-146 o C; 1 H MR (400 MHz, CDCl3) δ 7.58-7.52 (m, 2H), 7.25 (d, J = 8.8 Hz, 1H), 7.10-7.07 (m, 1H), 6.97 (d, J = 7.6 Hz, 1H), 6.70 (s, 1H), 3.35-3.25 (m, 4H), 2.05-1.93 (m, 4H); 13 C MR (100 MHz, CDCl3) δ 25.45, 47.80, 104.78, 110.45 (d, J 2 = 20.6 Hz), 116.26 (d, J 3 = 25.6 Hz), 116.73, 126.20, 127.67 (d, J 4 = 8.2 Hz), 127.95 (d, J 5 = 4.9 Hz), 132.17, 145.39, 157.97 (d, J 1 = 239 Hz); IR(neat): 707, 791, 803, 839, 859, 1136, 1237, 1392, 1508, 1566, 1605, 2837, 2971 cm -1 ; HRMS (ESI): [M+H] + calcd for C14H14F, 216.1183; found, 216.1182. Diethyl-phenanthren phenanthren-3-yl yl-amine (3p) 6 Et 2 3p Yellow solid; m.p. 42-43 o C; 1 H MR (400 MHz, CDCl3) δ 8.60 (d, J = 8.0 Hz, 1H), 7.84 (dd, J = 7.2, 2.0 Hz, 1H), 7.80 (d, J = 2.4 Hz, 1H), 7.74 (d, J = 8.8 Hz, 1H), 7.62-7.53 (m, 3H), 7.46 (d, J = 8.8 Hz, 1H), 7.13 (dd, J = 8.8, 2.4 Hz, 1H), 3.57 (q, J = 6.8 Hz, 4H), 1.30 (t, J = 6.8 Hz, 6H); 13 C MR (100 MHz, CDCl3) δ 12.64, 44.72, 102.51, 114.42, 122.22, 122.50, 123.36, 125.48, 126.13, 126.70, 128.45, 129.54, 129.58, 131.81, 132.76, 146.63; IR(neat): 820, 1010, 1143, 1255, 1355, 1454, 1518, 1611, 2926, 2965 cm -1 ; HRMS (ESI): [M+H] + calcd for C18H19, 250.1590; found, 250.1590. 1-Phenanthren Phenanthren-3-yl yl-pyrrolidine (3q)

S11 3q Purple solid; m.p. 138-139 o C; 1 H MR (300 MHz, CDCl3) δ 8.63 (d, J = 7.5 Hz, 1H), 7.86 (dd, J = 7.2, 2.4 Hz, 1H), 7.76 (d, J = 8.7 Hz, 1H), 7.65-7.54 (m, 4H), 7.48 (d, J = 9.0 Hz, 1H), 7.15 (dd, J = 8.7, 2.4 Hz, 1H), 3.52-3.47 (m, 4H), 2.12-2.08 (m, 4H); 13 C MR (75 MHz, CDCl3) δ 25.51, 47.81, 101.94, 114.13, 121.89, 122.66, 123.31, 125.37, 126.12, 126.92, 128.38, 129.46, 129.55, 131.79, 132.76, 146.68; IR(neat): 743, 820, 1161, 1280, 1376, 1451, 1521, 1611, 2849, 2961 cm -1 ; HRMS (ESI): [M+H] + calcd for C18H17, 248.1434; found, 248.1434. 1-(4 (4-thyl thyl-naphthalen naphthalen-2-yl) yl)-pyrrolidine (3r) 7 3r Brown oil; 1 H MR (400 MHz, CDCl3) δ 7.84 (d, J = 8.4 Hz, 1H), 7.65 (d, J = 8.4 Hz, 1H), 7.39-7.35 (m, 1H), 7.26-7.19 (m, 1H), 6.88 (s, 1H), 6.65 (d, J = 1.6 Hz, 1H), 3.43-3.40 (m, 4H), 2.67 (s, 3H), 2.09-2.04 (m, 4H); 13 C MR (100 MHz, CDCl3) δ 19.67, 25.45, 47.72, 103.16, 116.55, 120.98, 123.91, 125.56, 125.87, 126.33, 135.13, 135.52, 145.53; IR(neat): 739, 765, 808, 1370, 1425, 1474, 1603, 1619, 2833, 2964, 3048 cm -1 ; HRMS (ESI): [M+H] + calcd for C15H17, 212.1434; found, 212.1435. 1-(4 (4-Phenyl Phenyl-naphthalen naphthalen-2-yl) yl)-pyrrolidine (3s) 3s Ph Yellow solid; m.p. 109-111 o C; 1 H MR (400 MHz, CDCl3) δ 7.73-7.69 (m, 2H), 7.56-7.42 (m, 5H), 7.38-7.35 (m, 1H), 7.14-7.10 (m, 1H), 6.97 (d, J = 2.4 Hz, 1H), 6.83 (d, J = 2.4 Hz, 1H), 3.46-3.43 (m, 4H), 2.09-2.06 (m, 4H); 13 C MR (100 MHz, CDCl3) δ 25.49, 47.82, 104.58, 116.80, 121.33, 124.64, 125.89, 126.07, 126.14, 127.09, 128.10, 130.00, 135.74, 141.17, 141.30, 145.22; IR(neat): 748, 776, 812, 1143, 1411, 1573, 1598, 1614, 2831 cm -1 ; HRMS (ESI): [M+H] + calcd for C20H19, 274.1590; found, 274.1589. 1-(6,7 (6,7-Dimethoxy Dimethoxy-4-methyl methyl-naphthalen naphthalen-2-yl) yl)-pyrrolidine (3t)

S12 4 OE OE OE H 3 H H 7 5 3t OE 8 H 2 OE 3t 6 H OE OE Experiment (see spectroscopy). White solid; m.p. 159-162 o C; 1 H MR (600 MHz, CDCl3) δ 7.09 (s, 1H), 6.99 (s, 1H), 6.74 (s, 1H), 6.58 (s, 1H), 3.98 (s, 6H), 3.37 (t, J = 6.7 Hz, 4H), 2.60 (s, 3H), 1.06 (t, J = 6.7 Hz, 4H); 13 C MR (100 MHz, CDCl3) δ 19.86, 25.38, 47.79, 55.61, 55.77, 102.93, 103.45, 105.41, 114.61, 120.34, 131.21, 133.57, 144.89, 146.02, 149.54; IR(neat): 840, 1158, 1247, 1416, 1509, 1608, 2825 cm -1 ; HRMS (ESI): [M+H] + calcd for C17H21O2, 272.1645; found, 272.1645. (6-Chloro Chloro-4-methyl methyl-naphthalen naphthalen-2-yl) yl)-diethyl diethyl-amine (3u) OE 7 OE 4 OE H H 6 H Et 2 3 Et 2 OE Cl H 5 Cl 8 H CH 3 OE 2 OE 3u 3u OE Experiment (see spectroscopy). Pale yellow oil; 1 H MR (400 MHz, CDCl3) δ 7.76 (d, J = 2.0 Hz, 1H), 7.52 (d, J = 8.8 Hz, 1H), 7.28 (d, J = 2.0 Hz, 1H), 6.96 (s, 1H), 6.70 (d, J =2.8 Hz, 1H), 3.45 (q, J = 6.8 Hz, 4H), 2.60 (s, 3H), 1.21 (t, J = 6.8 Hz, 6H); 13 C MR (100 MHz, CDCl3) δ 12.71, 19.73, 44.39, 103.68, 117.50, 122.90, 126.18, 126.53, 126.59, 127.93, 133.90, 134.54, 145.60; IR(neat): 671, 833, 1086, 1128, 1354, 1423, 1490, 1595, 1616, 2927, 2967 cm -1 ; HRMS (ESI): [M+H] + calcd for C15H18Cl, 248.1201; found, 248.1200. 1-(6 (6-Chloro Chloro-4-methyl methyl-naphthalen naphthalen-2-yl) yl)-pyrrolidine (3v) Cl 3v Cl 6 OE OE H 3 7 H H 4 5 H 8 H 2 OE OE 3v OE experiment (see spectroscopy). Slight red solid; m.p. 119-121 o C; 1 H MR (600 MHz, CDCl3) δ 7.78 (d, J = 2.0 Hz, 1H), 7.52 (d, J = 2.7 Hz, 1H), 7.28 (dd, J = 8.7, 2.1 Hz, 1H), 6.87 (s, 1H), 6.58 (s, 1H), 3.38 (t, J = 6.6 Hz,

S13 4H), 2.61 (s, 3H), 2.04 (t, J = 6.6 Hz, 4H); 13 C MR (75 MHz, CDCl3) δ 19.57, 25.45, 47.66, 102.87, 117.32, 123.01, 126.11, 126.20, 126.53, 127.78, 133.82, 134.45, 145.61; IR(neat): 836, 867, 1090, 1311, 1473, 1617, 2964 cm -1 ; HRMS (ESI): [M+H] + calcd for C15H16Cl, 246.1044; found, 246.1043. Diethyl-(4 (4-methyl methyl-naphthalen naphthalen-2-yl) yl)-amine (4w) 8 H 9 H Et 2 4w 5 OE H CH 3 2 OE H 4 Et 2 OE 3 OE 4w OE experiment (see spectroscopy). Yellow oil; 1 H MR (300 MHz, CDCl3) δ 8.25-8.22 (m, 1H), 7.73-7.70 (m, 1H), 7.43-7.38 (m, 1H), 7.32 (s, 1H), 6.97 (s, 1H), 3.19 (q, J = 7.2 Hz, 4H), 2.48 (s, 3H), 1.06 (t, J = 7.2 Hz, 6H); 13 C MR (100 MHz, CDCl3) δ 12.34, 21.94, 47.66, 120.06, 122.30, 124.08, 124.14, 125.65, 127.42, 129.42, 134.98, 135.02, 147.76; IR(neat): 740, 781, 841, 1069, 1405, 1574, 1597, 1625, 2930, 2968 cm -1 ; HRMS (ESI): [M+H] + calcd for C15H19, 214.1590; found, 214.1590. (6,7-Dimethoxy Dimethoxy-4-methyl methyl-naphthalen naphthalen-2-yl) yl)-diethyl diethyl-amine (4x) Et 2 4x OE 7 OE H H CH 3 2 OE H 6 9 H Et 2 OE OE 3 OE 4x OE experiment (see spectroscopy). Colrless oil; 1 H MR (400 MHz, CDCl3) δ 7.61 (s, 1H), 7.22 (s, 1H), 7.03 (s, 1H), 6.90 (s, 1H), 4.02 (s, 3H), 3.98 (s, 3H), 3.15 (q, J = 6.8 Hz, 4H), 2.45 (s, 3H), 1.06 (t, J = 6.8 Hz, 6H); 13 C MR (100 MHz, CDCl3) δ 12.65, 21.74, 47.95, 55.73, 55.73, 103.25, 106.05, 118.64, 121.24, 125.08, 130.55, 133.38, 146.65, 148.31, 149.37; IR(neat): 727, 764, 863, 1144, 1250, 1480, 1505, 1606, 2254, 2966 cm -1 ; HRMS (ESI): [M+H] + calcd for C17H23O2, 274.1802; found, 274.1801.

S14 1a CHO 1a CHO

S15 1b CHO 1b CHO

S16 F 1c CHO F 1c CHO

S17 CHO 1d CHO 1d

S18 O 1e O 1e

S19 O 1f Ph O 1f Ph

S20 1g O 1g O

S21 Cl 1h O Cl 1h O

S22 OHC 1i OHC 1i

S23 Et 2 3a Et 2 3a

S24 2 3b 2 3b

S25 3c 3c

S26 O 3d O 3d

S27 3e 3e

S28 3f 3f

S29 3g 3g

S30 3h 3h

S31 O 3i O 3i

S32 S 3j S 3j

S33 3k 3k

S34 Et 2 3l Et 2 3l

S35 3m 3m

S36 Et 2 F 3n Et 2 F 3n

S37 F 3o F 3o

S38 Et 2 3p Et 2 3p

S39 3q 3q

S40 3r 3r

S41 3s Ph 3s Ph

S42 3t OE 4 OE OE H 3 H H 7 5 OE 8 H 2 OE 3t 6 H OE

S43 3t

S44 Et 2 Cl 3u OE 6 H OE 7 4 H H OE Et 2 3 OE Cl 8 3u H CH 3 2 OE H 5 OE

S45 Et 2 Cl 3u

S46 Cl 3v 6 OE 7 H OE H 3 H 4 Cl 8 H 2 OE 3v 5 H OE

S47 Cl 3v

S48 4w Et 2 8 H 9 H 5 OE H CH 3 2 OE H 4 Et 2 OE 3 OE 4w

S49 4w Et 2

S50 4x Et 2 OE 7 H H OE CH 2 3 OE 9 H 4x Et 2 3 OE OE H 6 OE

S51 4x Et 2

S52 chanistic study (1): Crude 1 HMR spectra. OHC MS 4A Et 2 + + Et 2 H, RT OHC OHC OHC 1i 3b 3c 3d reaction time, 10 min: 3b:3c:3d = 88:0:12 O

S53 chanistic study (2): Crude 1 HMR spectra. OHC MS 4A Et 2 + + Et 2 H, RT OHC OHC OHC 1i 3b 3c 3d reaction time, 2 h: 3b:3c:3d = 9:73:18 O