Supporting Information Copyright Wiley-VC Verlag Gmb & Co. KGaA, 69451 Weinheim, 2009
Supporting Information for Graphite-Supported Gold anoparticles as Efficient Catalyst for Aerobic xidation of Benzylic Amines to Imines and -Substituted 1,2,3,4-Tetrahydroisoquinolines to Amides: Synthetic Applications and Mechanistic Study Man-o So, Yungen Liu, Chi-Ming o, and Chi-Ming Che* Department of Chemistry and pen Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of ong Kong, Pokfulam Road, ong Kong SAR, China. Part I. List of Figures P. 2 Part II. List of Tables P. 3 Part III. Characterization of Compounds P. 4 1
Part I. List of Figures Figure S1. Plot of reaction rate (Ro) against oxygen partial pressure (P 2 ) on the aerobic oxidation of dibenzylamine (1a) catalyzed by AuPs/C. Reaction conditions: dibenzylamine (0.4 mmol), AuPs/C (Au: 5 mol %), toluene (5 ml), 2 (0.1-1.0 atm) bubbling, 110 o C. 2
Part II. List of Tables Table S1. Listing of log k rel and σ values for the AuPs/C catalyzed aerobic oxidation of para-substituted -phenylbenzylamines. Y AuPs/C (Au: 5 mol %), 2 bubbling toluene, 1.5 h, 110 o C Y Entry Y log k rel σ 1 Me 0.622-0.268 2 Me 0.384-0.170 3 0 0 4 Cl -0.274 +0.226 5 CF 3-1.103 +0.540 3
Part III. Characterization of Compounds: Compound Reference C. A. ewman, J. C. Antilla, P. Chen, A. V. Predeus, L. Fielding, W. D. Wulff, J. Am. Chem. Soc. 2007, 129, 7216-7217. 2a Z. Zhu, J.. Espenson, J. Am. Chem. Soc. 1996, 118, 9901-9907. 2b J. L. G. Ruano, J. Alemán, I. Alonso, A. Parra, V. Marcos, J. Aguirre, Chem. Eur. J. 2007, 13, 6179-6195. 2c Z. Zhu, J.. Espenson, J. Am. Chem. Soc. 1996, 118, 9901-9907. 2e R. Torregrosa, I. M. Pastor, M. Yus, Tetrahedron 2005, 61, 11148-11155. Cl 2f M.. Ibrahim,. K. AL-Deeb, E-J. Chem. 2006, 3, 257-261. Br 2g 2h V. Koleva, T. Dudev, I. Wawer, J. Mol. Struct. 1997, 412, 153-159. M.. Ibrahim,. K. AL-Deeb, E-J. Chem. 2006, 3, 257-261 2i 2j Z. Zhu, J.. Espenson, J. Am. Chem. Soc. 1996, 118, 9901-9907. 4
M. J. Tomaszewski, J. Warkentin,.. Werstiuk, Aust. J. Chem. 1995, 48, 291-321. 2k K. C. icolaou, C. J.. Mathison, T. Montagnon, J. Am. Chem. Soc. 2004, 126, 5192-5201. 2l. aeimi, F. Salimi, K. Rabiei, J. Mol. Catal. A-Chem. 2006, 260, 100-104. Me 5 6 14a 2m 2p Me K. C. icolaou, C. J.. Mathison, T. Montagnon, J. Am. Chem. Soc. 2004, 126, 5192-5201. K. C. icolaou, C. J.. Mathison, T. Montagnon, J. Am. Chem. Soc. 2004, 126, 5192-5201. W. uang, J. Li, L. u, Synthetic Commun. 2007, 37, 2137-2143. J. Almena, F. Foubelo, M. Yus, Tetrahedron 1996, 52, 8545-8564. 14b C. Perrio-uard, C. Aubert, M.-C. Lasne, J. Chem. Soc., Perkin Trans. 1 2000, 311-316.. J. Kumpaty, S. Bhattacharyya, Synthesis 2005, 2205-2209. 14c 14d 14f C. Perrio-uard, C. Aubert, M.-C. Lasne, J. Chem. Soc., Perkin Trans. 1 2000, 311-316. C. Perrio-uard, C. Aubert, M.-C. Lasne, J. Chem. Soc., Perkin Trans. 1 2000, 311-316. A. P. Venkov, S. M. Statkova-Abeghe, Tetrahedron 1996, 52, 1451-1460. 15a 5
15c 15f K. rito, A. oribata, T. akamura,. Ushito,. agasaki, M. Yuguchi, S. Yamashita, M. Tokuda, J. Am. Chem. Soc. 2004, 126, 14342-14343. K. rito, A. oribata, T. akamura,. Ushito,. agasaki, M. Yuguchi, S. Yamashita, M. Tokuda, J. Am. Chem. Soc. 2004, 126, 14342-14343. A. P. Venkov, S. M. Statkova-Abeghe, Tetrahedron 1996, 52, 1451-1460. 16a A. P. Venkov, S. M. Statkova-Abeghe, Tetrahedron 1996, 52, 1451-1460. 16b A. P. Venkov, S. M. Statkova-Abeghe, Tetrahedron 1996, 52, 1451-1460. 16f Z. Li, C.-J. Li, J. Am. Chem. Soc. 2005, 127, 6968-6969. Ph 17 Z. Li, C.-J. Li, Eur. J. rg. Chem. 2005, 3173-3176. Ph Et Et 19 Z. Li, C.-J. Li, J. Am. Chem. Soc. 2005, 127, 6968-6969. Ph 22 Z. Li, C.-J. Li, J. Am. Chem. Soc. 2005, 127, 6968-6969. Ph 24 6
27a Me. Sharghi, M.. Beyzavi, M. M. Doroodmand, Eur. J. rg. Chem. 2008, 4126-4138. 27d 27e 27f Cl Br. Sharghi, M.. Beyzavi, M. M. Doroodmand, Eur. J. rg. Chem. 2008, 4126-4138.. Sharghi, M.. Beyzavi, M. M. Doroodmand, Eur. J. rg. Chem. 2008, 4126-4138. L.-. Du, Y.-G. Wang, Synthesis 2007, 675-678. 2. Sharghi, M.. Beyzavi, M. M. Doroodmand, Eur. J. rg. Chem. 2008, 4126-4138. 27g Cl. Sharghi, M.. Beyzavi, M. M. Doroodmand, Eur. J. rg. Chem. 2008, 4126-4138. Cl 27h D. Mizuno, K. Yamaguchi, Catal. Today 2008, 132, 18-26. 28 7
2d -(4-tert-butylbenzylidene)benzenamine (2d) Yellow oil. 1 MR (300 Mz, CDCl 3, 25 o C, TMS): δ = 8.42 (s, 1), 7.84 (d, 3 J(,) = 8.4 z, 2), 7.49 (d, 3 J(,) = 8.4 z, 2), 7.38 (m, 2), 7.21 (m, 3), 1.35 ppm (s, 9); 13 C MR (75 Mz, CDCl 3, 25 o C): δ = 160.7, 130.1, 129.5, 129.1, 126.4, 126.2, 126.1, 121.3, 35.4, 31.6 ppm; MS (EI) m/z 237 (M + ); RMS (EI) m/z for C 17 19 1 (M + ), calcd 237.1517, found 237.1515. 2 2n -(4-nitrobenzylidene)cyclohexanamine (2n) Yellow Solid. 1 MR (300 Mz, CDCl 3, 25 o C, TMS): δ = 8.39 (s, 1), 8.25 (d, 3 J(,) = 8.7 z, 2), 7.89 (d, 3 J(,) = 8.7 z, 2), 3.34 3.23 (m, 1), 1.90 1.53 (m, 7), 1.46 1.20 ppm (m, 3); 13 C MR (75 Mz, CDCl 3, 25 o C): δ = 156.6, 149.2, 142.6, 129.1, 124.2, 70.5, 34.6, 25.97, 25.96 ppm; MS (EI) m/z 232 (M + ); RMS (EI) m/z for C 13 16 2 2 (M + ), calcd 232.1212, found 232.1214. 2o -(4-methoxybenzylidene)cyclohexanamine (2o) Colourless liquid. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 8.24 (s, 1), 7.66 (d, 3 J(,) = 8.7 z, 2), 6.91 (d, 3 J(,) = 8.7 z, 2), 3.83 (s, 3), 3.18 3.10 (m, 1), 1.85 1.79 (m, 2), 1.75 1.64 (m, 3), 1.62 1.55 (m, 2), 1.39 1.19 ppm (m, 3); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 157.9, 129.6, 113.9, 69.9, 55.3, 34.5, 25.7, 24.9 ppm; MS (EI) m/z 217 (M + ); RMS (EI) m/z for C 14 19 1 1 (M + ), calcd 217.1467, found 217.1458. 8
2q -(4-tert-butylbenzylidene)(4-tert-butylphenyl)methanamine (2q) White solid. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 8.36 (s, 1), 7.71 (d, 3 J(,) = 8.4 z, 2), 7.43 (d, 3 J(,) = 8.4 z, 2), 7.36 (d, 3 J(,) = 8.4 z, 2), 7.26 (d, 3 J(,) = 8.4 z, 2), 4.78 (s, 2), 1.33 (s, 9), 1.31 ppm (s, 9); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 161.7, 154.1, 149.8, 136.4, 133.6, 128.1, 127.7, 125.5, 125.4, 64.8, 34.9, 34.5, 31.4, 31.2 ppm; MS (EI) m/z 307 (M + ); RMS (EI) m/z for C 22 29 1 (M + ), calcd 307.2300, found 307.2294. Me 8a 6-methoxyquinoline (8a) Yellow oil. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 8.64 (dd, J(,) = 4.2, 1.6 z, 1), 7.89 (d, 3 J(,) = 8.7 z, 2), 7.25 (dd, J(,) = 9.2, 2.8 z, 1), 7.22 7.18 (m, 1), 6.91 (d, 3 J(,) = 2.8 z, 1), 3.78 ppm (s, 3); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 157.7, 147.9, 144.4, 134.7, 130.8, 129.3, 122.2, 121.3, 105.1, 55.5 ppm; MS (EI) m/z 159 (M + ); RMS (EI) m/z for C 10 9 1 1 (M + ), calcd 159.0684, found 159.0682. 8b Quinoline (8b) Yellow oil. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 8.92 (dd, J(,) = 4.2, 1.7 z, 1), 8.17 8.11 (m, 2), 7.82 (m, 1), 7.74 7.69 (m, 1), 7.57 7.53 (m, 1), 7.40 ppm (dd, J(,) = 8.3, 4.2 z, 1); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 150.4, 148.2, 136.1, 129.5, 129.4, 128.3, 127.8, 126.6, 121.1 ppm; MS (EI) m/z 129 (M + ); RMS (EI) m/z for C 9 7 1 (M + ), calcd 129.0578, found 129.0575. 9
8c Indole (8c) White solid. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 7.79 (brs, 1), 7.63 (d, 3 J(,) = 7.8 z, 1), 7.26 (d, 3 J(,) = 8.1 z, 1), 7.20 7.14 (m, 1), 7.13 7.08 (m, 1), 7.04 7.02 (m, 1), 6.52 6.50 ppm (m, 1); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 135.8, 127.9, 124.4, 122.1, 120.8, 119.9, 111.2, 102.6 ppm; MS (EI) m/z 117 (M + ); RMS (EI) m/z for C 8 7 1 (M + ), calcd 117.0578, found 117.0581. 10 & 11 10. Yellow oil. 1 MR (500 Mz, CDCl 3, 25 o C, TMS): δ = 7.53 7.51 (m, 1), 7.21 7.17 (m, 2), 7.12 7.08 (m, 3), 7.07 7.03 (m, 1), 6.99 (d, 3 J(,) = 7.5 z, 1), 5.29 (s, 1), 4.52 (d, 3 J(,) = 9.6 z, 1), 4.04 (d, 3 J(,) = 9.6 z, 1), 3.88 3.77 (m, 2), 3.66 3.59 (m, 1), 3.52 3.45 (m, 1), 3.33 3.28 (m, 1), 3.23 3.07 (m, 3), 2.84 (dt, J(,) = 15.8, 2.9 z, 1), 2.57 (dt, J(,) = 16.7, 3.6 z, 1), 0.86 ppm (t, 3 J(,) = 7.1 z, 3); 13 C MR (125 Mz, CDCl 3, 25 o C): δ = 173.0, 136.3, 135.7, 135.4, 132.1, 128.42, 128.37, 127.2, 127.0, 126.7, 126.6, 125.1, 82.9, 66.6, 62.4, 60.5, 46.9, 44.4, 29.4, 22.7, 13.7 ppm; MS (EI) m/z 348 (M + ); RMS (EI) m/z for C 22 24 2 2 (M + ), calcd 348.1838, found 348.1812. 11. Yellow oil. 1 MR (500 Mz, CDCl 3, 25 o C, TMS): δ = 7.38 7.36 (m, 1), 7.29 7.22 (m, 2), 7.20 7.06 (m, 5), 5.09 (s, 1), 4.50 (d, 3 J(,) = 8.9 z, 1), 4.40 4.32 (m, 2), 3.66 (d, 3 J(,) = 9.0 z, 1), 3.25 3.20 (m, 1), 3.09 3.03 (m, 1), 2.95 2.83 (m, 3), 2.82 2.65 (m, 3), 1.37 ppm (t, 3 J(,) = 7.2 z, 3); 13 C MR (125 Mz, CDCl 3, 25 o C): δ = 174.2, 137.3, 134.8, 134.7, 132.4, 128.7, 128.4, 127.4, 126.8, 126.15, 126.07, 125.95, 79.4, 71.0, 64.9, 61.2, 49.9, 43.2, 29.5, 29.1, 14.3 ppm; MS (EI) m/z 348 (M + ); RMS (EI) m/z for C 22 24 2 2 (M + ), calcd 348.1838, found 348.1812. 10
13a 4,4-dimethyl-3,4,6,7-tetrahydro-1-pyrido[2,1-a]isoquinolin-2(11b)-one (13a) Yellow oil. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 7.18 7.11 (m, 3), 7.09 6.99 (m, 1), 4.23 (dd, 3 J(,) = 11.8, 3.4 z, 1), 3.27 3.21 (m, 1), 3.10 2.97 (m, 1), 2.87 2.79 (m, 2), 2.70 2.63 (m, 1), 2.61 2.47 (m, 2), 2.25 (dd, 3 J(,) = 13.5, 2.2 z, 1), 1.37 (s, 3), 1.10 ppm (s, 3); 13 C MR (125 Mz, CDCl 3, 25 o C): δ = 209.1, 137.9, 134.6, 128.8, 126.3, 126.1, 125.7, 57.7, 56.4, 53.9, 47.5, 41.2, 30.6, 30.1, 19.7 ppm; MS (EI) m/z 229 (M + ); RMS (EI) m/z for C 15 19 1 1 (M + ), calcd 229.1467, found 229.1458. 13b 1-(1,2,3,4-tetrahydroisoquinolin-1-yl)hexan-2-one (13b) Yellow oil. 1 MR (500 Mz, CDCl 3, 25 o C, TMS): δ = 7.27 7.12 (m, 2), 7.11 7.08 (m, 1), 7.06 7.03 (m, 1), 4.51 (dd, 3 J(,) = 8.5, 3.9 z, 1), 3.20 3.15 (m, 1), 3.03 2.97 (m, 1), 2.93 2.84 (m, 3), 2.77 2.71 (m, 1), 2.51 2.40 (m, 2), 1.62 1.55 (m, 2), 1.37 1.28 (m, 2), 0.91 ppm (t, 3 J(,) = 7.3 z, 3); 13 C MR (125 Mz, CDCl 3, 25 o C): δ = 210.8, 137.9, 135.5, 129.5, 126.2, 125.9, 125.6, 52.0, 49.5, 43.4, 41.1, 29.8, 25.8, 22.3, 13.9 ppm; MS (EI) m/z 231 (M + ); RMS (EI) m/z for C 15 21 1 1 (M + ), calcd 231.1623, found 231.1616. 13c 1-phenyl-2-(1,2,3,4-tetrahydroisoquinolin-1-yl)ethanone (13c) Yellow oil. 1 MR (500 Mz, CDCl 3, 25 o C, TMS): δ = 7.99 (d, 3 J(,) = 7.3 z, 2), 7.57 (t, 3 J(,) = 7.4 z, 1), 7.47 (t, 3 J(,) = 7.7 z, 2), 7.18 7.12 (m, 4), 4.74 (dd, 3 J(,) = 9.2, 3.2 z, 1), 3.54 (dd, J(,) = 17.6, 9.2 z, 1), 3.46 (dd, J(,) = 17.6, 3.2 z, 1), 3.26 3.20 (m, 1), 3.09 3.03 (m, 1), 2.96 2.89 (m, 1), 2.83 2.56 ppm (m, 1); 13 C MR (125 Mz, CDCl 3, 25 o C): δ = 199.4, 137.8, 137.0, 135.5, 133.3, 129.5, 128.7, 128.1, 126.3, 126.0, 125.8, 52.1, 45.5, 40.9, 29.7 ppm; MS (EI) m/z 251 (M + ); RMS (EI) m/z for C 17 17 1 1 (M + ), calcd 251.1310, found 251.1300. 11
14e 2-octyl-1,2,3,4-tetrahydroisoquinoline (14e) Yellow oil. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 7.13 7.07 (m, 3), 7.02 7.00 (m, 1), 3.62 (s, 2), 2.91 (t, 3 J(,) = 5.9 z, 2), 2.72 (t, 3 J(,) = 5.9 z, 2), 2.49 (t, 3 J(,) = 7.7 z, 2), 1.37 1.22 (m, 12), 0.88 ppm (t, 3 J(,) = 6.9 z, 3); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 128.6, 126.6, 126.0, 125.5, 58.6, 56.3, 51.0, 31.9, 29.6, 29.3, 29.1, 27.7, 27.2, 22.7, 14.1 ppm; MS (EI) m/z 245 (M + ); RMS (EI) m/z for C 17 27 1 (M + ), calcd 245.2143, found 245.2137. 15b 2-ethyl-3,4-dihydroisoquinolin-1(2)-one (15b) Yellow oil. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 8.08 (dd, 3 J(,) = 7.7, 1.2 z, 1), 7.43 7.37 (m, 1), 7.36 7.31 (m, 1), 7.16 (d, 3 J(,) = 7.4 z, 1), 3.63 (q, 3 J(,) = 7.2 z, 2), 3.55 (t, 3 J(,) = 6.7 z, 2), 2.99 (t, 3 J(,) = 6.6 z, 2), 1.22 ppm (t, 3 J(,) = 7.2 z, 3); 13 C MR (125 Mz, CDCl 3, 25 o C): δ = 164.1, 138.0, 131.4, 128.2, 127.0, 126.8, 45.5, 42.2, 28.2, 12.8 ppm; MS (EI) m/z 175 (M + ); RMS (EI) m/z for C 11 13 1 1 (M + ), calcd 175.0997, found 175.0993. 12
15d 2-butyl-3,4-dihydroisoquinolin-1(2)-one (15d) Yellow oil. 1 MR (300 Mz, CDCl 3, 25 o C, TMS): δ = 8.04 (dd, 3 J(,) = 7.6, 1.2 z, 1), 7.39 7.32 (m, 1), 7.31 7.25 (m, 1), 7.12 (d, 3 J(,) = 7.3 z, 1), 3.56 3.47 (m, 4), 2.93 (t, 3 J(,) = 6.6 z, 2), 1.61 1.52 (m, 2), 1.41 1.28 (m, 2), 0.92 ppm (t, 3 J(,) = 7.3 z, 3); 13 C MR (75 Mz, CDCl 3, 25 o C): δ = 164.1, 137.8, 131.3, 129.6, 128.0, 126.8, 126.7, 47.1, 45.9, 29.7, 28.1, 20.1, 13.8 ppm; MS (EI) m/z 203 (M + ); RMS (EI) m/z for C 13 17 1 1 (M + ), calcd 203.1310, found 203.1302. 15e 2-octyl-3,4-dihydroisoquinolin-1(2)-one (15e) Yellow oil. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 8.08 (dd, 3 J(,) = 7.6, 1.2 z, 1), 7.42 7.37 (m, 1), 7.35 7.30 (m, 1), 7.16 (d, 3 J(,) = 7.4 z, 1), 3.58 3.52 (m, 4), 2.97 (t, 3 J(,) = 6.6 z, 2), 1.65 1.58 (m, 2), 1.34 1.25 (m, 10), 0.87 ppm (t, 3 J(,) = 7.0 z, 3); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 164.2, 137.9, 131.4, 129.7, 128.2, 126.9, 126.7, 47.5, 46.0, 31.8, 29.4, 29.2, 28.2, 27.7, 27.0, 22.6, 14.1 ppm; MS (EI) m/z 259 (M + ); RMS (EI) m/z for C 17 25 1 1 (M + ), calcd 259.1936, found 259.1926. 16c 2-propylisoquinolin-1(2)-one (16c) Yellow oil. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 8.43 (d, 3 J(,) = 8.1 z, 1), 7.64 7.59 (m, 1), 7.51 7.44 (m, 2), 7.06 (d, 3 J(,) = 7.3 z, 1), 6.48 (d, 3 J(,) = 7.3 z, 1), 3.96 (t, 3 J(,) = 7.3 z, 2), 1.86 1.76 (m, 2), 0.98 ppm (t, 3 J(,) = 7.5 z, 3); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 162.1, 137.0, 132.0, 131.8, 127.8, 126.7, 125.8, 105.9, 50.9, 22.5, 11.2 ppm; MS (EI) m/z 187 (M + ); RMS (EI) m/z for C 12 13 1 1 (M + ), calcd 187.0997, found 187.0995. 13
16d 2-butylisoquinolin-1(2)-one (16d) Yellow oil. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 8.44 (d, 3 J(,) = 8.1 z, 1), 7.62 (t, 3 J(,) = 7.5 z, 1), 7.52 7.45 (m, 2), 7.06 (d, 3 J(,) = 7.3 z, 1), 6.49 (d, 3 J(,) = 7.3 z, 1), 4.01 (t, 3 J(,) = 7.4 z, 2), 1.81 1.73 (m, 2), 1.46 1.36 (m, 2), 0.96 ppm (t, 3 J(,) = 7.4 z, 3); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 162.2, 137.1, 132.1, 131.8, 127.9, 126.8, 125.9, 106.0, 49.3, 31.5, 20.1, 13.9 ppm; MS (EI) m/z 201 (M + ); RMS (EI) m/z for C 13 15 1 1 (M + ), calcd 201.1154, found 201.1144. 16e 2-octylisoquinolin-1(2)-one (16e) Yellow oil. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 8.44 (d, 3 J(,) = 8.1 z, 1), 7.62 (t, 3 J(,) = 7.5 z, 1), 7.52 7.45 (m, 2), 7.06 (d, 3 J(,) = 7.3 z, 1), 6.49 (d, 3 J(,) = 7.3 z, 1), 3.99 (t, 3 J(,) = 7.4 z, 2), 1.80 1.73 (m, 2), 1.40 1.21 (m, 10), 0.87 ppm (t, 3 J(,) = 6.8 z, 3); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 162.3, 137.1, 132.1, 131.8, 127.9, 126.8, 125.9, 106.0, 49.6, 31.9, 29.43, 29.38, 29.3, 26.9, 22.7, 14.2 ppm; MS (EI) m/z 257 (M + ); RMS (EI) m/z for C 17 23 1 1 (M + ), calcd 257.1780, found 257.1777. Ph CF 3 21 2-phenyl-1-(2-(4-(trifluoromethyl)phenyl)ethynyl)-1,2,3,4-tetrahydroisoquinoline (21) Yellow oil. 1 MR (400 Mz, CDCl 3, 25 o C, TMS): δ = 7.45 (d, 3 J(,) = 7.9 z, 2), 7.38 7.29 (m, 5), 7.26 7.17 (m, 3), 7.11 (d, 3 J(,) = 7.5 z, 2), 6.92 6.80 (m, 1), 5.65 (s, 1), 3.78 3.71 (m, 1), 3.68 3.59 (m, 1), 3.18 3.09 (m, 1), 3.00 2.94 ppm (m, 1); 13 C MR (100 Mz, CDCl 3, 25 o C): δ = 149.5, 134.9, 134.5, 132.1, 129.3, 129.1, 127.51, 127.47, 126.5, 125.15, 125.11, 125.08, 125.04, 120.0, 116.8, 91.4, 83.6, 52.5, 43.5, 29.0 ppm; MS (EI) m/z 377 (M + ); RMS (EI) m/z for C 24 18 F 3 1 (M + ), calcd 377.1391, found 377.1368. 14
27b Me Me 2-(3,4-dimethoxyphenyl)-1-benzimidazole (27b) White solid. 1 MR (400 Mz, CD 3 D, 25 o C, TMS): δ = 7.65 (d, 3 J(,) = 2.0 z, 1), 7.59 (dd, J(,) = 8.38, 1.0 z, 1), 7.51 7.48 (m, 2), 7.18 7.13 (m, 2), 7.01 (d, 3 J(,) = 8.4 z, 1), 3.88 (s, 3), 3.82 ppm (s, 3); 13 C MR (100 Mz, CD 3 D, 25 o C): δ = 153.5, 152.4, 150.8, 123.7, 120.9, 112.8, 111.2, 56.49, 56.45 ppm; MS (EI) m/z 254 (M + ); RMS (EI) m/z for C 15 14 2 2 (M + ), calcd 254.1055, found 254.1051. 27c 2-mesityl-1-benzimidazole (27c) White solid. 1 MR (400 Mz, CD 3 D, 25 o C, TMS): δ = 7.51 (brs, 2), 7.21 7.16 (m, 2), 6.92 (s, 2), 2.26 (s, 3), 2.03 ppm (s, 6); 13 C MR (100 Mz, CD 3 D, 25 o C): δ = 153.5, 140.7, 138.9, 129.4, 129.2, 123.5, 21.3, 19.9 ppm; MS (EI) m/z 236 (M + ); RMS (EI) m/z for C 16 16 2 (M + ), calcd 236.1313, found 236.1311. 15