Eur. J. Org. Chem WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007 ISSN X SUPPORTING INFORMATION

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1 Eur. J. Org. Chem WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007 ISSN X SUPPORTING INFORMATION Title: Effect of Varying the Anionic Component of a Copper(I) Catalyst on Homologation of Arylacetylenes to Allenes by the Mannich Reaction Author(s): Vipan Kumar, Alex Chipeleme, Kelly Chibale* Ref. No.: O

2 1. General. 2. General Method for the preparation of compounds 2a-d, 3a-d, 4b and 4d. 2.1 Synthetic Procedure and Characterization of 2a 2.2 Synthetic Procedure and Characterization of 2b 2.3 Synthetic Procedure and Characterization of 4a 2.4 Synthetic Procedure and Characterization of 4b 2.5 Synthetic Procedure and Characterization of 2c 2.6 Synthetic Procedure and Characterization of 2d 2.7 Synthetic Procedure and Characterization of 4c 2.8 Synthetic Procedure and Characterization of 4d 2.9 Synthetic Procedure and Characterization of 3a 2.10 Synthetic Procedure and Characterization of 3b 2.11 Synthetic Procedure and Characterization of 3c 2.12 Synthetic Procedure and Characterization of 3d 3. General Method for the preparation of compounds 10a-g and 11a-g. 3.1 Synthetic Procedure and Characterization of 10a 3.2 Synthetic Procedure and Characterization of 10b 3.3 Synthetic Procedure and Characterization of 10c 3.4 Synthetic Procedure and Characterization of 10d 3.5 Synthetic Procedure and Characterization of 10e 3.6 Synthetic Procedure and Characterization of 10f 3.7 Synthetic Procedure and Characterization of 10g 3.8 Synthetic Procedure and Characterization of 11a 3.9 Synthetic Procedure and Characterization of 11b 3.10 Synthetic Procedure and Characterization of 11c 3.11 Synthetic Procedure and Characterization of 11d 3.12 Synthetic Procedure and Characterization of 11e 3.13 Synthetic Procedure and Characterization of 11f 3.14 Synthetic Procedure and Characterization of 11g

3 1. General. 1 H NMR spectra were determined in CDCl 3 solution on a Varian Gemini (300 MHz) or a Varian Unity Spectrometer (400 MHz), using TMS as an internal standard. The chemical shift (δ) are given in ppm relative to TMS (δ = 0.00). The coupling constant J is given in Hz. 13 C NMR spectra were recorded on the same instruments at 75 MHz or 100 MHz in the same deuterated solvents using TMS as an internal inference. Mass spectra (EI) were recorded on a VG Micromass 16F spectrometer at 70eV with accelerating voltage of 4 Kv and accurate mass determinations were measured on a Kratos Limited MS9/50 spectrometer (at Cape Technikon, SA) and VG (Micromass) 70-SE magnetic sector mass spectrometer (at Kent, UK). Melting points were determined using a Reichert-Jung hot stage apparatus and are uncorrected. Infrared (IR) spectra were recorded in Nujol on a satellite FTIR spectrometer. Reactions were monitored by thin layer chromatography (tlc) using Merck F254 silica gel plates and visualized with uv light and either by staining with iodine vapors or spraying with 1% aqueous potassium permanganate solution containing 5% sodium hydroxide or 7% anisaldehyde in ethanol containing 1% sulfuric acid. Column chromatography and preparative layer chromatography (plc) were performed using Merck Kieselgel 60. All materials and dry solvents used in reactions were purchased from commercial suppliers and used without further purification unless otherwise stated. 2. General Method for the preparation of compounds 2a-d, 3a-d, 4b and 4d. A mixture of acetylenic chalcone (1.0 mmol), paraformaldehyde (2.5 mmol), amine (2.0 mmol) and anhydrous cuprous bromide or cupric chloride (0.5 mmol) in dry 1,4-dioxane (5.0 ml) was heated under reflux at 100 C for 3 h. The reaction mixture was cooled to room temperature and then filtered. The filtrate was poured into water and extracted with ether (3 10 ml). The combined ether extracts were concentrated to give a light brown solid residue, which was subjected to column chromatography on silica gel (10% EtOAc: hexane and MeOH:CHCl 3 : 17% NH 4 OH 2: 2: 1) to afford the title compounds 2a-d, 3a-d, 4b and 4d. 2.1 Synthetic Procedure and Characterization of 4-Propa-1,2-dienyl-benzaldehyde (2a) Method, which gave 2a as a brown oil (0.012g, 14%); IRν max (Nujol)/cm (C=C), 1680 (C=O), 1960 (C=C=C); δ H (300 MHz; CDCl 3 ) δ 5.23 (2H, d, J 6.6, CH=C=CH 2 ), 6.22 (1H, t, J 6.6, CH=C=CH 2 ), 7.44 (2H, d, J 8.4, H-3/5), 7.81 (2H, d, J8.4, H-2/6), 9.96 (1H, s, CHO); δ c (75 MHz; CDCl 3 ) 79.4, 93.7, (2C), (2C), 135.0, 140.8, 191.6, 211.0; HRMS (EI) m/z Found: M +, Calc. For C 10 H 8 O: M, Synthetic Procedure and Characterization of 1-(4-Propa-1,2-dienyl-phenyl)-ethanone (2b) Method, which gave 2b as a light-yellow oil (0.016g, 35%); IRν max (Nujol)/cm (C=C), 1660 (C=O), 1955 (C=C=C); δ H (400 MHz; CDCl 3 ) 5.21 (2H, d, J 6.8, CH=C=CH 2 ), 6.20 (1H, t, J 6.6, CH=C=CH 2 ), 7.36 (2H, d, J 8.4, H-3/5), 7.89 (2H, d, J 8.4, H-2/6); δ c (100 MHz; CDCl 3 ) 23.4, 79.2, 93.6, (2C), (2C), 135.6, 139.2, 197.4, 210.8; LRMS (EI) m/z (%), 158 ([M] +, 35), 143 ([M-CH 3 ] +, 41), 129 (([M-CH 3 -CH 2 ]+, 2), 115 ([M-CH 3-2CH 2 ]+, 26) 2.3 Synthetic Procedure and Characterization of 1-{4-[4-(4-Acetyl-phenyl)-buta-1,3-diynyl]- benzaldehyde 4a The conditions employed for the preparation of this compound were those described in general method, which gave 4a as a pale yellow solid (0.016g, 32%); mp o C (from ethyl acetate-hexane); IRν max (Nujol)/cm (C=C), 1680 (C=O), 2120 (C C), δ H (400 MHz; CDCl 3 ) 7.69 (4H, d, J 8.0, H- 3/5), 7.87 (4H, d, J 8.0, H-2/6), (2H, s, CHO); δ c (100 MHz; CDCl 3 ) 26.1 (2C), 82.4 (2C), 85.6 (2C), 123.2, 128.1, 129.0, 133.1, 136.7, 137.6, (2C); HRMS (EI) m/z Found: M +, Calc. For C 18 H 10 O 2 : M, Synthetic Procedure and Characterization of 1-{4-[4-(4-Acetyl-phenyl)-buta-1,3-diynyl]-phenyl}- ethanone 4b The conditions employed for the preparation of this compound were those described in general method, which gave 4b as a pale yellow solid (0.032g, 72%); mp o C (from ethyl acetate-hexane); IRν max (Nujol)/cm (C=C), 1670 (C=O), 2125 (C C), δ H (300 MHz; CDCl 3 ) 2.61 (6H, s), 7.62

4 (4H, d, J 7.6, H-3/5), 7.94 (4H, d, J 7.6, H-2/6 ); δ c (75 MHz; CDCl 3 ) 26.6 (2C), 82.0 (2C), 85.4 (2C), (2C), (4C), (4C), (2C), (2C); LRMS (EI) m/z (%), 286 ([M] +, 100), 271 ([M-CH 3 ] +, 73), 228 ([M-2CH 3 -CO] +, 36). 2.5 Synthetic Procedure and Characterization of 3-(4-Propa-1,2-dienyl-phenyl)-1-[4-(tetrahydropyran-2-ylmethyl)-phenyl]-propenone 2c Method, which gave 2c as a brown solid (0.019g, 34%); mp o C (from ethyl acetate-hexane); IRν max (Nujol)/cm (C-O), 1594 (C=C), 1660 (C=O); 1950 (C=C=C); δ H (300 MHz; CDCl 3 ) 1.66 (3H, m, H-4 /5a ), 1.88 (2H, m, H-3a /5b ), 1.99 (1H, m, H-3b ), 3.62 (1H, m, H-6a ), 3.88 (1H, m, H-6b ), 5.20 (2H, d, J 6.9, CH=C=CH 2 ), 5.54 (1H, t, J 3.0, H-2 ), 6.18 ((1H, t, J 6.9, CH=C=CH 2 ), 7.13 (2H, d, J 9.0, H-3/5), 7.33 (2H, d, J 8.4, H-2 /6 ), 7.51 (1H, d, J 15.6, H-α), 7.58 (2H, d, J 8.4, H-3 /5 ), 7.77 (1H, d, J 15.6, H-β), 8.01 (2H, d, J 9.0, 2/6); δ c (75 MHz; CDCl 3 ) 18.5, 25.1, 30.1, 62.0, 79.1, 93.8, 96.1, 116.1(2C), 121.4, (2C), (2C), 130.6, (2C), 133.7, 136.3, 143.6, 160.9, 188.8, 210.5; HRMS (EI) m/z Found: M +, Calc. For C 23 H 22 O: M, Synthetic Procedure and Characterization of 1-(4-Propa-1,2-dienyl-phenyl)-3-[4-(tetrahydropyran-2-ylmethyl)-phenyl]-propenone 2d Method, which gave 2d as a brown solid (0.012g, 20%); mp o C (from ethyl acetate-hexane); IRν max (Nujol)/cm (C-O), 1590 (C=C), 1660 (C=O), 1950 (C=C=C); δ H (300 MHz; CDCl 3 ) 1.66 (3H, m, H-4 /5a ), 1.88 (2H, m, H-3a /5b ), 2.00 (1H, m, H-3b ), 3.63 (1H, m, H-6a ), 3.88 (1H, m, H-6b ), 5.22 (2H, d, J 6.6, CH=C=CH 2 ), 5.48 (1H, t, J 3.0, H-2 ), 6.22 (1H, t, J 6.6, CH=C=CH 2 ), 7.09 (2H, d, J 8.7, H-3 /5 ), 7.40 (2H, d, J 8.7, H-2 /6 ), 7.44 (1H, d, J 15.6, H-α), 7.59 (2H, d, J 8.4, H-3/5), 7.78 (1H, d, J 15.6, H-β), 7.97 (2H, d, J 8.4, 2/6); δ c (75 MHz; CDCl 3 ) 18.5, 25.1, 30.2, 62.0, 79.1, 93.8, 96.1, (2C), 121.4, 127.1, (2C), (2C), (2C), 133.7, 136.4, 144.4, 159.1, 189.7, 210.8; HRMS (EI) m/z Found: M +, Calc. For C 23 H 22 O 3 : M, Synthetic Procedure and Characterization of 1-[4-(tetrahydro-pyran-2-yloxy)-phenyl]-3-{4-[4-(4- {3--[4-(tetrahydro-pyran-2-yloxy)-phenyl]- acryloyl}-phenyl)-buta-1,3-divinyl]-phenyl}-propenone 4c Method, which gave 4c as a pale Orange (0.008g, 13%); mp C (from ethyl acetate-hexane); IRν max (Nujol)/cm -1 ), 1030 (C-O),1660 (C=O), 2250 (C C); δ H (400 MHz; CDCl 3 ) (6H, m, H- 4 /5a ), (4H, m, H-3a /5b ), (2H, m, H-3b ), 3.63 (2H, m, H-6a ), (2H, m, H-6b ), 5.49 (2H, br s, H-2 ), 7.09 (4H, d, J 8.4, H-3/5) 7.38 (2H, d, J 15.6, H-α), 7.59 (4H, d, J 8.4, H-2 /6 ), 7.65 (4H, d, J 8.4, H-3 /5 ), 7.79 (2H, d, J 15.6, H-β), 7.98 (4H, d, J 8.4, H-2/6); δ c (100 MHz; CDCl 3 ) 18.5 (2C), 25.0 (2C), 30.1 (2C), 62.0 (2C), 82.1 (2C), 89.0 (2C), 96.2 (2C), (4C), (2C), (2C), (4C), (2C), (4C), (4C), (2C), (2C), (2C), (2C); LRMS (EI) m/z (%), 663 ([M+ H] +, 2), 579 ([M-(THP+H)] +, 10), 85 ([THP+H] +, 100). 2.8 Synthetic Procedure and Characterization of 3-[4-(tetrahydro-pyran-2-yloxy)-phenyl]-1-{4-[4-(4- {3--[4-(tetrahydro-pyran-2-yloxy)-phenyl]- acryloyl}-phenyl)-buta-1,3-divinyl]-phenyl}-propenone 4d Method, which afforded 4d as a pale Orange (0.011g, 30 %); mp C (from ethyl acetatehexane); IRν max (Nujol)/cm (C-O), 1659 (C=O), 2254 (C C); δ H (300 MHz; CDCl 3 ) (6H, m, H-4 /5a ), (4H, m, H-3a /5b ), (2H, m, H-3b ), 3.63 (2H, m, H-6a ), (2H, m, H-6b ), 5.49 (2H, br s, H-2 ), 7.09 (4H, d, J 8.8, H-3 /5 ) 7.39 (2H, d, J 15.2, H-α), 7.59 (4H, d, J 8.8, H-2 /6 ), 7.65 (4H, d, J 8.4, H-2/6), 7.79 (4H, d, J 15.2, H-β), 7.99 (4H, d, J 8.4, H- 3/5); δ c (75 MHz; CDCl 3 ) {18.5, 25.0, 30.1, 62.0, 82.1, 89.0, 96.2, (2C), 119.5, 125.6, (2C), 128.4, (2C), (2C), 138.6, 145.3, 159.3, 189.4} x 2; LRMS (EI) m/z (%), 662 ([M] +, 6), 579 ([M-(THP+H)] +, 15), 85 ([THP+H] +, 100). 2.9 Synthetic Procedure and Characterization of 4-(3-Diisopropylamino-prop -1-ynyl)-benzaldehyde 3a Method, which afforded 3a as brown crystals (0.077g, 90%); mp C (from chloroform: hexane); R f = 0.34 (30% EtOAc/ Hexane); IRν max (Nujol)/cm (C-O), 1594 (C=C), 1680 (C=O),

5 2253 (C C); δ H (300 MHz; CDCl 3 ) 1.13 (12H, d, J 6.6, N[CH(CH 3 ) 2 ] 2 ), 3.23 (2H, sep, J 6.6, N[CH(CH 3 ) 2 ] 2 ), 3.65 (2H, s, C CCH 2 ), 7.50 (2H, d, J 8.1, H-3/5a, 7.77 (2H, d, J 8.1, H-2/6), 9.96 (1H, s, CHO); δ c (75 MHz; CDCl 3 ) 20.6 (4C), 34.9, 48.6 (2C), 82.7, 93.9, 129.4, (2C), (2C), 135.1, 191.3; HRMS (EI) m/z Found: M +, Calc. For C 16 H 21 NO: M, Synthetic Procedure and Characterization of 1-[4-(3-Diisopropylamino-prop-1-ynyl)-phenyl]- ethanone 3b Method C, which afforded 3b as a brownish oil (0.066g, 36%). R f = 0.22 (30% EtOAc/hexane); IRν max (Nujol)/cm (C-O), 1594 (C=C), 1680 (C=O), 2253 (C C); δ H (300 MHz; CDCl 3 ) 1.20 (12H, d, J 6.6, N[CH(CH 3 ) 2 ] 2 ), 2.61 (3H, s, COCH 3 ), 3.23 (2H, sep, J 6.6, N[CH(CH 3 ) 2 ] 2 ), 3.78 (2H, s, C CCH 2 ), 7.45 (2H, d, J 8.1, H-3/5a, 7.86 (2H, d, J 8.1, H-2/6); δ c (75 MHz; CDCl 3 ) 20.2 (4C), 26.5, 34.8, 49.2 (2C), 83.7, 91.4, 128.3, (2C), (2C), 136.1, 197.2; HRMS (EI) m/z Found: M +, Calc. For C 17 H 23 NO: M, Synthetic Procedure and Characterization of 3-[4-(3-Diisopropylamino-prop-1-ynyl)-phenyl)-1- (4-(tetrahydro-pyran-2-yloxy)-phenyl]-propenone 3c Method, which afforded 3c as a yellow solid (0.065g, 93%); mp C (from ethyl acetate-hexane); R f = 0.14 (30% EtOAc/ Hexane); IRν max (Nujol)/cm (C-O), 1600 (C=C), 1680 (C=O), 2251 (C C); δ H (400 MHz; CDCl 3 ) 1.17 (12H, d, J 6.4 Hz, NCH[CH 3 ] 2 ), 1.69 (3H, m, H-5a /4 ), 1.90 (2H, m, H-3a /5b ), 2.01 (1H, m, H-3b ), 3.29 (2H, sep, J 6.4 Hz, N[CH(CH 3 ) 2 ]), 3.65 (1H, m, H-6a ), 3.68 (1H, s, C CCH 2 ), 3.88 (1H, m, H-6b ), 5.54 (1H, t, J 3.2, H-2 ), 7.13 (2H, d, J 8.8, H-3/5), 7.42 (2H, d, J 8.0, H-2 /6 ), 7.50 (1H, d, J 15.6, H-α), 7.55 (2H, d, J 8.0, H-3 /5 ), 7.75 (1H, d, J 15.6, H-β), 8.01 (2H, d, J 8.8, H-2/ 6); δ c (75 MHz; CDCl 3 ) 18.5, 20.8 (4C), 25.3, 30.3, 35.2(2C), 49.0, 62.3, 80.2, 83.6, 96.1, (2C), 122.5, 126.0, (2C), 130.8, (2C), (2C), 136.7, 143.3, 161.2, 188.9; HRMS (EI) m/z Found: M +, Calc. For C 29 H 35 O 2 N: M, Synthetic Procedure and Characterization of 1-[4-(3-Diisopropylamino-prop-1-ynyl)-phenyl]-3- [4-(tetrahydro-pyran-2-yloxy)-phenyl]-propenone 3d Method, which gave 3d as a yellow solid (0.014g, 36%); mp C (from ethyl acetate-hexane); R f = 0.17 (30% EtOAc/ Hexane); IR ν max (Nujol)/cm (C=C), 1680 (C=O), 2245 (C C); δ H (400 MHz; CDCl 3 ) 1.17 (12H, d, J 6.4 Hz, NCH[CH 3 ] 2 ), 1.66 (3H, m, H-5a /4 ), 1.88 (2H, m, H- 3a /5b ), 2.01 (1H, m, H-3b ), 3.29 (2H, sep, J 6.4 Hz, N[CH(CH 3 ) 2 ]), 3.64 (1H, m, H-6a ), 3.68 (1H, s, C CCH 2 ), 3.88 (1H, m, H-6b ), 5.49 (1H, t, J 3.2, H-2 ), 7.09 (2H, d, J 8.8, H-3 /5 ) 7.38 (1H, d, J 15.6, H-α), 7.59 (2H, d, J 8.8, H-2 /6 ), 7.60 (2H, d, J 8.8, H-3/5), 7.78 (1H, d, J 15.6, H-β), 7.96 (2H, d, J 8.8, H-2/6); δ c (100 MHz; CDCl 3 ) 18.5, 20.7 (4C), 25.2, 30.1, 35.2 (2C), 48.9, 62.5, 80.3, 83.6, 96.2, (2C), 123.5, 126.2, (2C), 131.1, (2C), (2C), 136.5, 143.2, 162.2, 188.7; HRMS (EI) m/z Found: M +, Calc. For C 29 H 35 O 2 N: M, General Method for the preparation of compounds 10a-g and 11a-g. A mixture of aryl acetylene (1.0 mmol), paraformaldehyde (2.5 mmol), amine (2.0 mmol) and anhydrous cuprous bromide or cupric chloride or Cu(OAc) 2 (0.5 mmol) in dry 1,4-dioxane (5.0 ml) was heated under reflux at 100 C for 3 h. The reaction mixture was cooled to room temperature and then filtered. The filtrate was poured into water and extracted with ether (3 10 ml). The combined ether extracts were concentrated to give a light brown solid residue, which was subjected to column chromatography on silica gel (5% EtOAc: hexane and 10% EtOAc: hexane) to afford the title compounds 10a-g and 11a-g. 3.1 Synthetic Procedure and Characterization of N,N-diisopropyl-3-phenylprop-2-yn-1-amine (10a) Method, which gave 10 a as a colourless oil: δ H (400 MHz; CDCl 3 ) (d, 12H, J = 6.56 Hz, 2x-CH(CH 3 ) 2 ); (m, 2H, 2x-CH(CH 3 ) 2 ); 3.62 (s, 2H, -CH 2 ); 7.23-

6 7.26 (m, 3H, ArH); (m, 2H, ArH) δ C (100 MHz) 20.7, 34.8, 48.5, 83.4, 89.1, 123.8, 127.6, 128.1, Analysis calculated for C 15 H 21 N Calculated C, 83.67; H, 9.83; N, 6.50 Found 83.21; H, 9.98; N, m/z 215 (M + ) 3.2 Synthetic Procedure and Characterization of N,N-diisopropyl-3-p-tolylprop-2-yn-1- amine (10b): The conditions employed for the preparation of this compound were those described in General Method, which gave 10b as a colourless oil: δ H (400 MHz; CDCl 3 ) (d, 12H, J = 6.8Hz, 2x-CH(CH 3 ) 2 ); 2.30 (s, 3H, -CH 3 ); (m, 2H, 2x- CH(CH 3 ) 2 ); 3.61 (s, 2H, -CH 2 ); (d, 2H, J = 8.4Hz, ArH); (d, 2H, J = 8.4Hz, ArH) δ C (100MHz): 20.7, 21.4, 34.8, 48.5, 83.5, 88.3, 120.8, 128.9, 131.3, Analysis calculated for C 16 H 23 N Calculated C, 83.79; H, 10.11; N, 6.11 Found C, 84.21; H, 9.88; N, m/z 229 (M + ) 3.3 Synthetic Procedure and Characterization of 3-(4-bromophenyl)-N,Ndiisopropylprop-2-yn-1-amine (10c): The conditions employed for the preparation of this compound were those described in General Method, which gave 10c as a pale yellow oil: δ H (300 MHz; CDCl 3 ) (d, 12H, J = 6.3Hz, 2x-CH(CH 3 ) 2 ); (m, 2H, 2x-CH(CH 3 ) 2 ); 3.62 (s, 2H, -CH 2 ); (d, 2H, J = 8.4Hz, ArH); (d, 2H, J = 8.1Hz, ArH) δ C (100MHz): 20.6, 34.8, 48.6, 82.4, 90.5, 121.8, 122.7, 131.4, Analysis calculated for C 15 H 20 BrN Calculated: C, 61.23; H, 6.85; N, 4.76 Found: C, 60.56; H, 5.16; N, m/z 293 (M + ) 3.4 Synthetic Procedure and Characterization of N,N-diisopropyl-3-(2- methoxyphenyl)prop-2-yn-1-amine (10d): The conditions employed for the preparation of this compound were those described in General Method, which gave 10d as a pale yellow oil: δ H (300 MHz; CDCl 3 ) (d, 12H, J = 6.3Hz, 2x- CH(CH 3 ) 2 ); (m, 2H, 2x-CH(CH 3 ) 2 ); 3.72 (s, 2H, -CH 2 ); 3.84 (s, 3H, - OCH 3 ); (m, 2H, ArH); (m, 1H, ArH); (m, 1H, ArH) δ C (100MHz): 20.6, 35.0, 48.5, 55.6, 79.9, 92.9, 110.6, 113.0, 120.3, 128.9, 133.2, Analysis calculated for C 16 H 23 NO Calculated: C, 78.32; H, 9.45; N, 5.71 Found: C, 78.03; H, 9.76; N, m/z 245 (M + ) 3.5 Synthetic Procedure and Characterization of N,N-diisopropyl-3-(4- methoxyphenyl)prop-2-yn-1-amine (10e): The conditions employed for the preparation of this compound were those described in General Method, which gave 10e as a pale yellow oil: δ H (300 MHz; CDCl 3 ) (d, 12H, J = 6.3Hz, 2x- CH(CH 3 ) 2 ); (m, 2H, 2x-CH(CH 3 ) 2 ); 3.63 (s, 2H, -CH 2 ); 3.79 (s, 3H, - OCH 3 ); (d, 2H, J = 9.0Hz, ArH); (d, 2H, J = 8.7Hz, ArH) δ C (100MHz): 20.7, 34.8, 48.5, 55.2, 83.2, 87.5, 113.8, 116.0, 132.7, Analysis calculated for C 16 H 23 NO Calculated: C, 78.32; H, 9.45; N, 5.71 Found: C, 77.98; H, 9.22; N, m/z 245 (M + ) 3.6 Synthetic Procedure and Characterization of N,N-diisopropyl-3-(2-nitrophenyl)prop-2-yn- 1-amine (10f): The conditions employed for the preparation of this compound were those described in General Method, which gave 10f as a yellow oil: δ H (300 MHz; CDCl 3 ) (d, 12H, J = 6.8Hz, 2x-CH(CH 3 ) 2 ); (m, 2H, 2x- CH(CH 3 ) 2 ); 3.71(s, 2H, -CH 2 ); (d, 2H, J = 9.2 Hz, ArH); (d, 2H, J = 9.2 Hz, ArH) δ C (100MHz): 20.5, 34.9, 48.8, 82.0, 94.8, 123.3, 130.4, 131.9,

7 Analysis calculated for C 15 H 20 N 2 O 2 Calculated C, 69.20; H, 7.74; N, Found C, 68.88; H, 7.93; N, m/z 260 (M + ) 3.7 Synthetic Procedure and Characterization of 4-(3-(diisopropylamino)prop-1- ynyl)benzonitrile (10g): The conditions employed for the preparation of this compound were those described in General Method, which gave 10g as creamish white solid: m.p C, δ H (400 MHz; CDCl 3 ) (d, 12H, J = 6.6 Hz, 2x- CH(CH 3 ) 2 ); (m, 2H, 2x-CH(CH 3 ) 2 ); 3.66 (s, 2H, -CH 2 ); (d, 2H, J = 8.61Hz, ArH); (d, 2H, J = 8.64Hz, ArH) δ C (100MHz): 20.6, 34.9, 48.6, 82.0, 94.4, 111.0, 118.5, 128.7, 131.8, Analysis calculated for C 16 H 20 N 2 Calculated: C, 79.96; H, 8.39; N, Found : C, 79.24; H, 8.27; N, m/z 240 (M + ) 3.8 Synthetic Procedure and Characterization of 1,4-diphenylbuta-1,3-diyne (11a): The conditions employed for the preparation of this compound were those described in General Method, which gave 11a as pale yellow solid: m.p C, δ H (400 MHz; CDCl 3 ) (m, 6H, 2x3ArH); (m, 4H, 2x2ArH) δ C (100MHz): 73.9, 81.6, 121.8, 128.4, 129.2, Analysis Calculated for C 16 H 10 Calculated: C, 95.02; H, 4.98 Found: C, 94.05; H, 5.30 m/z 202 (M + ) 3.9 Synthetic Procedure and Characterization of 1,4-di-p-tolylbuta-1,3-diyne (11b): The conditions employed for the preparation of this compound were those described in General Method, which gave 11b as white solid: m.p C, δ H (400 MHz; CDCl 3 ) 2.33 (s, 6H, 2x-CH 3 ); (d, 4H, J = 8.02Hz, ArH); (d, 4H, J = 8.02Hz, ArH) δ C (100MHz): 21.6, 73.5, 81.5, 118.8, 129.2, 132.4, Analysis Calculated for C 18 H 14 Calculated C, 93.87; H, 6.13 Found C, 92.93; H, 6.20 m/z 230 (M + ) 3.10 Synthetic Procedure and Characterization of 1,4-bis(4-bromophenyl)buta-1,3-diyne (11c): The conditions employed for the preparation of this compound were those described in General Method, which gave 11c as pale yellow solid. m.p C δ H (400 MHz; DMSO-d 6 ) (d, 4H, J = 8.4Hz, ArH); (d, 4H, J = 8.4Hz, ArH) Analysis Calculated for C 16 H 8 Br 2 Calculated: C, 53.37; H, 2.24 Found: C, 52.67; H, 2.50 m/z 359 (M + ) 3.11 Synthetic Procedure and Characterization of 1,4-bis(2-methoxyphenyl)buta-1,3- diyne (11d): The conditions employed for the preparation of this compound were those described in General Method, which gave 11d as creamish white solid. m.p C, δ H (300 MHz; CDCl 3 ) 3.88 (s, 6H, 2x-OCH 3 ); (m, 4H, 2x2ArH); (m, 2H, 2x1ArH); (m, 2H, 2x1ArH) δ C (100MHz): 55.8, 78.0, 78.6, 110.7, 111.4, 120.5, 130.5, 134.4, Analysis Calculated for C 18 H 14 O 2 Calculated: C, 82.42; H, 5.38 Found: 81.62; H, 5.40 m/z 262 (M + ) 3.12 Synthetic Procedure and Characterization of 1,4-bis(4-methoxyphenyl)buta-1,3- diyne (11e): The conditions employed for the preparation of this compound were those described in General Method, which gave 11e as creamish white solid. m.p C δ H (300 MHz; CDCl 3 ) 3.81 (s, 6H, 2x-OCH 3 ); (d, 4H, J = 9.0Hz, ArH); (d, 4H, J = 8.7Hz, ArH) δ C (100MHz): 55.3, 72.9, 81.2, 113.9, 114.1, 134.0, Calculated: C, 82.42; H, 5.38 Found: C, 81.82; H, 5.39 m/z 262 (M + )

8 3.13 Synthetic Procedure and Characterization of 1,4-bis(2-nitrophenyl)buta-1,3-diyne (11f): The conditions employed for the preparation of this compound were those described in General Method, which gave 11f as dark brown solid. m.p C δ H (300 MHz; CDCl 3 ) (m, 2H, ArH); (dt, 2H, J = 1.31, 7.69 Hz ArH); (dd, 2H, J = 1.46, 7.74 Hz, ArH); (dd, 2H, J = 1.23, 8.24 Hz, ArH) Analysis Calculated for C 16 H 8 N 2 O 4 Calculated C, 65.76; H, 2.76; N, 9.59 Found: 65.55; H, 2.65; N, 9.03 m/z 292 (M + ) 3.14 Synthetic Procedure and Characterization of 4,4'-(buta-1,3-diyne-1,4-diyl)dibenzonitrile (11g): The conditions employed for the preparation of this compound were those described in General Method, which gave 11g as light brown soild. m.p C δ H (300 MHz; CDCl 3 ) (d, 4H, J = 8.6Hz, ArH); (d, 4H, J = 8.8 Hz, ArH); δ C (100MHz): 74.6, 76.9, 112.3, 115.7, 127.0, 131.8, Analysis Calculated for C 18 H 8 N 2 Calculated C, 85.70; H, 3.20; N, Found C, 85.89; H, 2.98; N, m/z 252 (M + )