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Electronic Supplementary Information
A CuBr-Mediated Expedient Synthesis of 4-Bromoisoquinolones from 2-Alkynylbenzaldehydes and Primary Amines under an O2 atmosphere
Pei Chui Too and Shunsuke Chiba*
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore
Fax: +65-67911961; E-mail: [email protected]
1. General S2 2. Synthesis of 2-alkynylbenzaldehyde derivatives 2.1. Preparation of 2-alkynylbenzaldehyde 1a-b & 1k-1s S2
2.2. Preparation of 2-arylethynylbenzaldehyde 1c-1j S6
3. CuBr-mediated synthesis of 4-bromoisoquinolones S9 3.1. A typical procedure for synthesis of 3aa S9 3.2. The reactions with CuCl and CuI S19 3.3. The reactions with !-alanine ethyl ester (2m) and propargylamine 2n S21 4. Control experiments to elucidate the reaction mechanism S22 5. 1H and 13C NMR spectrum of new compounds S24
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1. General 1H NMR (400MHz) spectra were recorded on a Bruker Avance 400 spectrometers in CDCl3
[using (CH3)4Si (for 1H, ! = 0.00) as internal standard]. 13C NMR (100 MHz) spectra on a Bruker Avance 400 spectrometers in CDCl3 [using CDCl3 (for 13C, ! = 77.00) as internal standard]. The following abbreviations were used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, qn = quintet, m = multiplet, brs = broad singlet, brd = broad doublet. IR spectra were recorded on a Shimazu IR Prestige-21 FT-IR Spectrometer. High-resolution mass spectra were obtained with a Finnigan MAT 95 XP mass spectrometer (Thermo Electron Corporation). Melting points were uncorrected and were recorded on a Buchi B-54 melting point apparatus.
Flash column chromatography was performed using Merck silica gel 60 with distilled solvents. Benzene was used without further purification. CuBr!SMe2 (99%) was purchased from Sigma-Aldrich Co., Inc. All amines 2 were purchased from Sigma-Aldrich Co., Inc. except for 2f,1 2m2 and 2n3. 2. Synthesis of 2-alkynylbenzaldehyde derivatives 2.1. Preparation of 2-alkynylbenzaldehyde 1a-b & 1k-1s: a typical procedure for synthesis of 2-(2-phenylethynyl)benzaldehyde (1a).
H
O
Br
H
O
Ph
Ph
2 mol % PdCl2(PPh3)21 mol % CuI
NEt3, 50 °C, 3-6 h+
1a To a solution of 2-bromobenzaldehyde (3.70 g, 20.0 mmol), PdCl2(PPh3)2 (0.28 g, 0.40 mmol), and CuI (38 mg, 0.20 mmol) in 80 mL of NEt3 was added phenylacetylene (2.08 g, 20.4 mmol). The resulting mixture was heated under nitrogen atmosphere at 50 °C. After the reaction was completed, the reaction mixture was quenched with distilled water and extracted with ethyl acetate (50 mL " 3). The combined extracts were washed with brine and dried over MgSO4. Volatile materials were removed in vacuo and the resulting crude material was purified by flash column chromatography (Si gel, hexane : ethyl acetate = 95 : 5) to give 2-(2-phenylethynyl)benzaldehyde (1a) in 94% yield. 2-(2-Phenylethynyl)benzaldehyde (1a)4 Brown oil; 1H NMR (400 MHz, CDCl3) ! 7.36-7.40 (3H, m), 7.45 (1H, tt, J = 0.8, 7.6 Hz), 7.55-7.60 (3H, m), 7.64 (1H, dd, J = 0.8, 7.6 Hz), 7.95 (1H, dd, J = 0.8, 7.6 Hz), 10.65 (d, J = 0.4 Hz); 13C NMR (100 MHz, CDCl3) ! 84.8, 96.3, 122.3, 126.8, 127.2, 128.5, 128.6, 129.0, 131.6, 133.2, 133.7, 135.8, 191.7. 2-[2-(4-Methoxyphenyl)ethynyl]benzaldehyde (1b)5 1 R. F. Nystrom, J. Am. Chem. Soc. 1953, 75, 292. 2 A. Rayan, M. Falah, U.S. Pat. Appl. Publ. 20100284959, 2010. 3 M. Lemhadri, H. Doucet, M. Santelli, Synthesis 2005, 1359. 4 J. H. Park, S. V. Bhilare, S. W. Youn, Org. Lett. 2011, 13, 2228. 5 S. Obika, H. Kono, Y. Yasui, R. Yanada, Y. Takemoto, J. Org. Chem. 2007, 72, 4462.
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Prepared from 2-bromobenzaldehyde and 1-ethynyl-4-methoxybenzene, and purified by by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in quantitative yield; White solid; 1H NMR (400 MHz, CDCl3) ! 3.84 (3H, s), 6.91 (2H, td, J = 2.4, 8.8 Hz), 7.42 (1H, dt, J = 0.4, 7.2 Hz), 7.50 (2H, td, J = 2.4, 8.8 Hz), 7.56 (1H, dt, J = 1.6, 7.6 Hz), 7.61 (1H, dd, J = 0.8, 7.2 Hz), 7.93 (1H, dd, J = 0.8, 8.0 Hz), 10.64 (1H, d, J = 0.8 Hz); 13C NMR (100 MHz, CDCl3) ! 55.3, 83.7, 96.6, 114.1, 114.3, 127.1, 127.3, 128.2, 133.0, 133.2, 133.7, 135.6, 160.2, 191.8. 2-(Hept-1-ynyl)benzaldehyde (1k)6
Prepared from 2-bromobenzaldehyde and 1-heptyne and purified by by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in 89% yield; Yellow oil; 1H NMR (400 MHz, CDCl3) ! 0.93 (3H, t, J = 7.2 Hz), 1.32-1.49 (4H, m), 1.65 (2H, tt, J = 6.8, 7.6 Hz), 2.48 (2H, t, J = 7.2 Hz), 7.35-7.40 (1H, m), 7.48-7.55 (2H, m), 7.89 (1H, d, J = 8.0 Hz), 10.54 (1H, d, J = 0.4 Hz); 13C NMR (100 MHz, CDCl3) ! 13.9, 19.5, 22.1, 28.2, 31.1, 76.3, 98.2, 126.8, 127.8, 127.9, 133.2, 133.6, 135.9, 192.2. 2-(Cyclohexylethynyl)benzaldehyde (1l)7
Prepared from 2-bromobenzaldehyde and andcyclohexylacetylene, and purified by by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in quantitative yield; Yellow oil; 1H NMR (400 MHz, CDCl3) ! 1.32-1.45 (3H, m), 1.46-1.61 (3H, m), 1.71-1.80 (2H, m), 1.87-1.95 (2H, m), 2.68 (1H, m), 7.35-7.40 (1H, m), 7.48-7.54 (2H, m), 7.88 (1H, d, J = 7.6 Hz), 10.56 (1H, d, J = 0.8 Hz); 13C NMR (100 MHz, CDCl3) ! 24.8, 25.8, 29.8, 32.4, 76.2, 102.1, 126.8, 127.8, 128.0, 133.2, 133.6, 135.8, 192.2. 2-(2-Cyclopropylethynyl)benzaldehyde (1m)4 6 A. Hamze, O. Provot, M. Alami, J.-D. Brion, Org. Lett. 2005, 7, 5625. 7 A. K. Verma, V. Rustagi, T. Aggarwal, A. P. Singh, J. Org. Chem. 2010, 75, 7691.
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Prepared from 2-bromobenzaldehyde and cyclopropylacetylene, and purified by by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in quantitative yield; Yellow oil; 1H NMR (400 MHz, CDCl3) ! 0.83-0.90 (2H, m), 0.90-0.98 (2H, m), 1.48-1.56 (1H, m), 7.36 (1H, t, J = 7.6 Hz), 7.46-7.53 (2H, m), 7.87 (1H, d, J = 8.0 Hz), 10.49 (1H , s); 13C NMR (100 MHz, CDCl3) ! 0.3, 8.9, 71.4, 101.2, 126.9, 127.7, 127.8, 133.2, 133.6, 136.0, 192.1. 3-Methyl-2-(phenylethynyl)benzaldehyde (1n)
Prepared from 2-bromo-3-methylbenzaldehyde and phenylacetylene, and purified by by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in 96% yield; Brown solid; mp. 48–50 °C; IR (neat) 691, 756, 1242, 1489, 1682, 1701 cm-1; 1H NMR (400 MHz, CDCl3) ! 2.59 (3H, s), 7.35 (1H, t, J = 7.6 Hz), 7.38-7.42 (3H, m), 7.50 (1H, d, J = 7.6 Hz), 7.56-7.60 (2H, m), 7.80 (1H, dd, J = 0.4, 8.0 Hz), 10.69 (1H, d, J = 0.8 Hz); 13C NMR (100 MHz, CDCl3) ! 20.5, 83.6, 100.8, 122.6, 124.6, 126.6, 128.1, 128.5, 129.0, 131.5, 134.8, 136.0, 141.5, 192.3; ESIHRMS: Found: m/z 221.0964. Calcd for C16H13O: (M+H)+ 221.0966. 4,5-Dimethoxy-2-(2-phenylethynyl)benzaldehyde (1o)4
Prepared from 6-bromo-1,3-benzodioxole-5-carboxaldehyde and phenylacetylene, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in 93% yield; White solid; 1H NMR (400 MHz, CDCl3) ! 6.10 (2H, s), 7.03 (1H, s), 7.37 (1H, s), 7.36-7.40 (3H, m), 7.52-7.56 (2H, m), 10.49 (1H, s); 13C NMR (100 MHz, CDCl3) ! 84.7, 95.1, 102.4, 106.1, 112.0, 122.3, 123.6, 128.5, 129.0, 131.6, 132.1, 148.7, 152.4, 190.0. 5-Methoxy-2-(phenylethynyl)benzaldehyde (1p)4
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Prepared from 2-bromo-5-methoxybenzaldehyde and phenylacetylene, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in 95% yield; Brown solid; 1H NMR (400 MHz, CDCl3) ! 3.88 (3H, s), 7.14 (1H, dd, J = 2.8, 8.8 Hz), 7.35-7.39 (3H, m), 7.43 (1H, d, J = 2.8 Hz), 7.53-7.58 (3H, m), 10.62 (1H, s); 13C NMR (100 MHz, CDCl3) ! 55.6, 84.8, 94.8, 109.8, 119.6, 121.7, 122.6, 128.5, 128.7, 131.5, 134.5, 137.2, 159.8, 191.6. 5-Fluoro-2-(phenylethynyl)benzaldehyde (1q)5
Prepared from 2-bromo-5-fluorobenzaldehyde and phenylacetylene, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in 91% yield; Pale yellow solid; 1H NMR (400 MHz, CDCl3) ! 7.30 (1H, dt, J = 2.8, 8.0 Hz), 7.37-7.41 (3H, m), 7.54-7.57 (2H, m), 7.60-7.67 (2H, m), 10.60 (1H, d, J = 3.2 Hz); 13C NMR (100 MHz, CDCl3) ! 83.8, 96.0, 113.7 (d, J = 22.9 Hz), 121.3 (d, J = 22.5 Hz), 122.1, 123.0 (d, J = 3.6 Hz), 128.5, 129.1, 131.6, 135.2 (d, J = 7.6 Hz), 137.7 (d, J = 6.5 Hz), 162.3 (d, J = 251.2 Hz), 190.4. 3-(Phenylethynyl)benzofuran-2-carbaldehyde (1r)
Prepared from 3-bromobenzofuran-2-carbaldehyde and phenylacetylene, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in 96% yield; Brown solid; mp. 99–101 °C; IR (neat) 685, 748, 881, 1294, 1339, 1667 cm-1; 1H NMR (400 MHz, CDCl3) ! 7.40-7.46 (4H, m), 7.58 (1H, dt, J = 1.2, 8.8 Hz), 7.60-7.66 (3H, m), 7.89 (1H, d, J = 8.0 Hz), 10.13 (1H, s); 13C NMR (100 MHz, CDCl3) ! 77.1, 100.1, 112.8, 115.9, 121.8, 122.5, 124.5, 127.5, 128.6, 129.6, 130.0, 131.9, 152.5, 155.4, 178.0; ESIHRMS: Found: m/z 247.0761. Calcd for C17H11O2: (M+H)+ 247.0759. 2-(Phenylethynyl)nicotinaldehyde (1s)5
Prepared from 2-bromonicotinaldehyde and phenylacetylene, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 80:20) in 88% yield; Brown solid; 1H NMR (400 MHz, CDCl3) ! 7.37-7.44 (4H, m), 7.64 (2H, d, J = 6.8 Hz), 8.20 (1H, d, J = 7.6 Hz), 8.81 (1H, d, J = 4.4 Hz), 10.66 (1H, s); 13C NMR (100 MHz, CDCl3) ! 84.6, 95.9, 121.1, 123.1, 128.4, 129.7, 131.6, 132.0, 134.6, 145.8, 154.3, 190.6.
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2.2. Preparation of 2-arylethynylbenzaldehyde 1c-1j: a typical procedure for the synthesis of 2-[2-(4-methylphenyl)ethynyl]benzaldehyde (1c)
To a solution of 2-ethynylbenzaldehyde1 (195 mg, 1.5 mmol), PdCl2(PPh3)2 (21 mg, 0.03 mmol), and CuI (2.9 mg, 0.015 mmol) in 6 mL of NEt3 was added the 1-iodo-4-methylbenzene (393 mg, 1.8 mmol). The resulting mixture was heated under nitrogen atmosphere at 50 °C. After the reaction was completed, the reaction mixture was quenched with distilled water and extracted with ethyl acetate (50 mL " 3). Volatile materials were removed in vacuo and the crude material was purified by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) to give 2-[2-(4-methylphenyl)ethynyl]benzaldehyde (1c) in 85% yield. 2-[2-(4-Methylphenyl)ethynyl]benzaldehyde (1c)8 Yellow solid; 1H NMR (400 MHz, CDCl3) ! 2.39 (3H, s), 7.19 (2H, d, J = 8.0 Hz), 7.43 (1H, tt, J = 0.8, 7.2 Hz), 7.46 (2H, d, J = 8.0 Hz), 7.57 (1H, dt, J = 1.6, 7.6Hz), 7.63 (1H, dd, J = 0.8, 7.6 Hz), 7.94 (1H, dd, J = 0.8, 7.6 Hz), 10.65 (1H, d, J = 0.8 Hz); 13C NMR (100 MHz, CDCl3) ! 21.6, 84.3, 96.6, 119.2, 127.1, 128.4, 129.3, 131.6 (overlapped), 133.1, 133.7, 135.7, 139.4, 191.8. 2-[2-(4-Fluorophenyl)ethynyl]benzaldehyde (1d)
Prepared from 2-ethynylbenzaldehyde and 4-fluoroiodobenzene, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in 82% yield; White solid; mp. 79–81 °C; IR (neat) 758, 829, 1233, 1506, 1591, 1684 cm-1; 1H NMR (400 MHz, CDCl3) ! 7.08 (2H, tt, J = 2.0, 8.8 Hz), 7.46 (1H, t, J = 7.6 Hz), 7.53-7.61 (3H, m), 7.63 (1H, dd, J = 0.8, 7.6 Hz), 7.95 (1H, dd, J = 0.8, 7.6 Hz), 10.62 (1H, d, J = 0.4 Hz); 13C NMR (100 MHz, CDCl3) ! 84.6, 95.2, 155.9 (d, J = 21.9 Hz), 118.4 (d, J = 3.5 Hz), 126.6, 127.4, 128.7, 133.2, 133.6 (d, J = 8.5 Hz), 133.8, 135.8, 162.9 (d, J = 249.6 Hz), 191.5; ESIHRMS: Found: m/z 225.0711. Calcd for C15H10FO: (M+H)+ 225.0716. Ethyl 4-((2-formylphenyl)ethynyl)benzoate (1e)9
8 J. D. Tovar, T. M. Swager, J. Org. Chem. 1999, 64, 6499. 9 C. P. Allen, T. Benkovics, A. K. Turek, T. P. Yoon, J. Am. Chem. Soc. 2009, 131, 12560.
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Prepared from 2-ethynylbenzaldehyde and ethyl 4-iodobenzoate, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 90:10) in 86% yield; Pale yellow solid; 1H NMR (400 MHz, CDCl3) ! 1.42 (3H, t, J = 7.2 Hz), 4.40 (2H, q, J = 7.2 Hz), 7.50 (1H, t, J = 7.6 Hz), 7.59-7.65 (3H, m), 7.67 (1H, dd, J = 0.8, 7.2 Hz), 7.97 (1H, dd, J = 0.8, 7.6 Hz), 8.06 (2H, td, J = 1.6, 8.4 Hz), 10.64 (1H, s); 13C NMR (100 MHz, CDCl3) ! 14.3, 61.2, 87.6, 95.3, 126.1, 126.8, 127.5, 129.1, 129.6, 130.6, 131.5, 133.4, 133.8, 135.9, 165.9, 191.3. 2-[2-(4-Trifluoromethylphenyl)ethynyl]benzaldehyde (1f)5
Prepared from 2-ethynylbenzaldehyde and 1-iodo-4-(trifluoromethyl)benzene, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in 74% yield; Pale yellow solid; 1H NMR (400 MHz, CDCl3) ! 7.50 (1H, t, J = 7.6 Hz), 7.61 (1H, dt, J = 1.2, 7.6 Hz), 7.63-7.70 (5H, m), 7.97 (1H, dd, J = 1.2, 7.6 Hz), 10.62 (1H, d, J = 0.8 Hz); 13C NMR (100 MHz, CDCl3) ! 87.2, 94.5, 123.8 (q, J = 270.6 Hz), 125.5 (q, J = 3.7 Hz), 125.8, 126.1, 127.6, 129.2, 130.7 (q, J = 32.7 Hz), 131.9, 133.4, 133.8, 136.0, 191.2. 2-[2-(3-Methoxyphenyl)ethynyl]benzaldehyde (1g)10
Prepared from 2-ethynylbenzaldehyde and 1-bromo-3-methoxybenzene, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 90:10) in 88% yield; Brown oil; 1H NMR (400 MHz, CDCl3) ! 3.84 (3H, s), 6.95 (1H, ddd, J = 0.8, 2.4, 8.4 Hz), 7.08 (1H, q, J = 1.2 Hz), 7.16 (1H, d, J = 7.6 Hz), 7.29 (1H, t, J = 7.6 Hz), 7.45 (1H, t, J = 7.6 Hz), 7.58 (1H, dt, J = 1.2, 7.6 Hz), 7.65 (1H, d, J = 7.6 Hz), 7.95 (1H, dd, J = 0.8, 7.6 Hz), 10.65 (1H, s); 13C NMR (100 MHz, CDCl3) ! 55.3, 84.6, 96.2, 115.7, 116.3, 123.3, 124.2, 126.8, 127.2, 128.6, 129.6, 133.2, 133.8, 135.8, 159.4, 191.7. 2-[2-(2-Methoxyphenyl)ethynyl]benzaldehyde (1h)11 10 N. T. Patil, A. Konala, V. Singh, V. V. N. Reddy, Eur. J. Org. Chem. 2009, 5178.
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Prepared from 2-ethynylbenzaldehyde and 1-bromo-2-methoxybenzene, and purified by by flash column chromatography (Si gel, hexane:ethyl acetate = 90:10) in 87% yield; Pale yellow solid; 1H NMR (400 MHz, CDCl3) ! 3.92 (3H, s), 6.92 (1H, d, J = 8.0 Hz), 6.96 (1H, t, J = 7.2 Hz), 7.35 (1H, dt, J = 1.6, 8.0 Hz), 7.42 (1H, t, J = 7.6 Hz), 7.51 (1H, dd, J = 1.6, 7.2 Hz), 7.56 (1H, dt, J = 1.2, 7.6 Hz), 7.65 (1H, dd, J = 0.4, 8.0 Hz), 7.95 (1H, dd, J = 0.8, 7.6 Hz), 10.74 (1H, d, J = 0.8 Hz); 13C NMR (100 MHz, CDCl3) ! 55.8, 89.0, 93.0, 110.6, 111.6, 120.5, 126.9, 127.4, 128.3, 130.5, 132.9, 133.2, 133.6, 135.8, 160.4, 192.5. 2-[2-(2-Bromophenyl)ethynyl]benzaldehyde (1i)12
Prepared from 2-ethynylbenzaldehyde and 2-bromoiodobenzene, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in 94% yield; White solid; 1H NMR (400 MHz, CDCl3) ! 7.24 (1H, dt, J = 1.6, 7.6 Hz), 7.34 (1H, dt, J = 1.2, 7.6 Hz), 7.48 (1H, t, J = 7.6 Hz), 7.58-7.63 (2H, m), 7.64 (1H, dd, J = 0.8, 8.0 Hz), 7.70 (1H, dd, J = 0.8, 8.0 Hz), 7.97 (1H, dd, J = 1.2, 8.0 Hz), 10.76 (1H, s); 13C NMR (100 MHz, CDCl3) ! 89.3, 94.6, 124.6, 125.8, 126.4, 127.1, 127.2, 129.0, 130.1, 132.6, 133.4, 133.5, 133.8, 136.1, 191.9. 2-[2-(2-Naphthyl)ethynyl]benzaldehyde (1j)
Prepared from 2-ethynylbenzaldehyde and 2-iodonaphthalene, and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 95:5) in 67% yield; White solid; mp. 73–75 °C; IR (neat) 743, 758, 1263, 1506, 1591, 1653, 1690 cm-1; 1H NMR (400 MHz, CDCl3) ! 7.48 (1H, t, J = 7.6 Hz), 7.51-7.56 (2H, m), 7.58-7.64 (2H. m), 7.70 (1H, dd, J = 0.8, 8.0 Hz), 7.83-7.88 (3H, m), 7.98 (1H, dd, J = 0.8, 8.0 Hz), 8.11 (1H, s), 10.73 (1H, d, J = 0.4 Hz); 13C NMR (100 MHz, CDCl3) ! 85.2, 96.8, 119.5, 126.8, 126.9, 127.1, 127.3, 127.8, 127.9, 128.0, 128.2, 128.6, 131.9, 132.9,
11 M. Alfonsi, M. Dell’Acqua, D. Facoetti, A. Arcadi, G. Abbiati, E. Rossi, Eur. J. Org. Chem. 2009, 2852–2862 12 D. P. Iwaniuk, C. Wolf, Org. Lett. 2011, 13, 2602.
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133.1, 133.2, 133.8, 135.8, 191.7; ESIHRMS: Found: m/z 257.0964. Calcd for C19H13O: (M+H)+ 257.0966. 3. CuBr-mediated synthesis of 4-bromoisoquinolones: 3.1. A typical procedure for synthesis of 3aa (Table 1, entry 6).
CuBr•SMe2(2.2 equiv)
benzene-pyridine(5 : 1)
SiO2, 80 °Cunder O2 (1 atm)
H
Ph
H2N Ph+N
O
Ph
PhBr3aa1a
2a(3 equiv)
O
To a stirred solution of 2-alkynylbenzaldehyde (1a) (105.0 mg, 0.509 mmol), CuBr!SMe2 (230.2 mg, 1.12 mmol) and SiO2 (0.3 g) in 5 mL of solvent (benzene : pyridine = 5 : 1) at 80 °C under O2 atmosphere were added benzylamine (2a) [(55 µL " 3), (0.509 " 3) mmol] three times at every 1 h interval, and the reaction mixture was allowed to stir for another 1 h. After cooled to room temperature, the reaction was quenched with pH 9 buffer and extracted with ethyl acetate (20 mL " 3). The combined extracts were washed with brine and dried over MgSO4. Volatile materials were removed in vacuo, and the resulting crude material was purified by flash column chromatography (Si gel, hexane:ethyl acetate = 90:10) to give 2-benzyl-4-bromo-3-phenylisoquinolin-1(2H)-one (3aa) (158.0 mg, 0.405 mmol) in 80% yield.
2-Benzyl-4-bromo-3-phenylisoquinolin-1(2H)-one (3aa) Sticky yellow oil; IR (neat) 694, 752, 1337, 1582, 1607, 1647 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.16 (2H, brs), 6.80-6.86 (2H, m), 7.06 (2H, d, J = 7.2 Hz), 7.13-7.18 (3H, m), 7.35 (2H, dd, J = 7.2, 7.6 Hz), 7.42 (1H, t, J = 7.2 Hz), 7.58 (1H, dt, J = 0.8, 7.6 Hz), 7.76 (1H, dt, J = 1.2, 7.6 Hz), 8.00 (1H, d, J = 8.0 Hz), 8.55 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 49.9, 102.8, 125.5, 126.5, 126.7, 127.0, 127.7, 128.2, 128.4, 128.5, 129.2, 129.4, 133.3, 135.5, 135.6, 137.1, 142.2, 162.1; ESIHRMS: Found: m/z 390.0490. Calcd for C22H17NO 79Br: (M+H)+ 390.0494. –Table 2– 4-Bromo-2-(4-methoxybenzyl)-3-phenylisoquinolin-1(2H)-one (3ab)
Yellow oil; IR (neat) 748, 1032, 1177, 1246, 1510, 1582, 1607, 1647 cm-1; 1H NMR (400 MHz, CDCl3) ! 3.74 (3H, s), 5.10 (2H, brs), 6.69 (2H, td, J = 1.6, 8.8 Hz), 6.76 (2H, d, J = 8.8 Hz), 7.09 (2H, d, J = 7.2 Hz), 7.39 (2H, t, J = 7.6 Hz), 7.45 (1H, t, J = 7.6 Hz), 7.59 (1H, ddd, J = 0.8, 7.2, 8.0 Hz), 7.78 (1H, ddd, J = 1.2, 7.2, 8.0 Hz), 8.01 (1H, d, J = 8.0 Hz), 8.55 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 49.4, 55.2, 102.8, 113.6, 125.6, 126.5, 127.7, 128.35, 128.41, 128.5, 129.2, 129.3, 129.6, 133.3, 135.6, 135.7, 142.2, 158.7, 162.2; ESIHRMS: Found: m/z 420.0599. Calcd for C23H19NO2
79Br: (M+H)+ 420.0599.
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4-Bromo-2-(4-methylbenzyl)-3-phenylisoquinolin-1(2H)-one (3ac)
Yellow oil; IR (neat) 692, 907, 1034, 1246, 1510, 1647 cm-1; 1H NMR (400 MHz, CDCl3) ! 2.27 (3H, s), 5.11 (2H, brs), 6.73 (2H, d, J = 8.0 Hz), 6.97 (2H, d, J = 8.0 Hz), 7.09 (2H, d, J = 6.8 Hz), 7.38 (2H, dd, J = 6.8, 7.6 Hz), 7.44 (1H, tt, J = 1.2, 7.6 Hz), 7.60 (1H, ddd, J = 1.2, 7.2, 7.6 Hz), 7.78 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.01 (1H, d, J = 8.0 Hz), 8.55 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 21.0, 49.8, 102.7, 125.6, 126.5, 126.7, 127.7, 128.4, 128.5, 128.9, 129.2, 129.5, 133.2, 134.1, 135.5, 135.7, 136.6, 142.3, 162.1; ESIHRMS: Found: m/z 404.0650. Calcd for C23H19NO 79Br: (M+H)+ 404.0650. 4-Bromo-2-(4-fluorobenzyl)-3-phenylisoquinolin-1(2H)-one (3ad)
Yellow solid; mp. 149–151 °C; IR (neat) 750, 1219, 1335, 1508, 1582, 1638 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.13 (2H, brs), 6.77-6.88 (4H, m), 7.07 (2H, d, J = 7.2 Hz), 7.39 (2H, dd, J = 7.2, 8.0 Hz), 7.46 (1H, tt, J = 1.2, 7.2 Hz), 7.61 (1H, ddd, J = 0.8, 7.2, 8.0 Hz), 7.79 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.02 (1H, d, J = 8.4 Hz), 8.55 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 49.2, 102.9, 115.0 (d. J = 21.4 Hz), 125.5, 126.6, 127.8, 128.4, 128.5, 128.7 (d. J = 8.0 Hz), 129.3, 129.5, 132.9 (d, J = 3.1 Hz), 133.3, 135.51, 135.53, 141.9, 161.9 (d, J = 244.2 Hz), 162.1; ESIHRMS: Found: m/z 408.0403. Calcd for C22H16NOF 79Br: (M+H)+ 408.0399. 4-Bromo-2-phenethyl-3-phenylisoquinolin-1(2H)-one (3ae)
White solid; mp. 121–123 °C; IR (neat) 754, 1223, 1337, 1508, 1584, 1609, 1651 cm-1; 1H NMR (400 MHz, CDCl3) ! 2.83-2.90 (2H, m), 3.95-4.03 (2H, m), 6.86 (2H, d, J = 6.4 Hz), 7.13-7.20 (3H, m), 7.27-7.32 (2H, m), 7.53-7.57 (3H, m), 7.60 (1H, dd, J = 7.2, 7.6 Hz), 7.78 (1H, dd, J = 7.6, 8.0 Hz), 8.00 (1H, d, J = 8.4 Hz), 8.54 (1H, d, J = 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 34.7, 49.1, 102.4, 125.6, 126.4, 126.5, 127.7, 128.1, 128.4, 128.7, 128.8, 129.3, 129.4, 133.2, 135.4, 136.0, 138.1, 142.0, 161.7; ESIHRMS: Found: m/z 404.0649. Calcd for C23H19NO 79Br: (M+H)+ 404.0650. 4-Bromo-2-(2,2-diphenylethyl)-3-phenylisoquinolin-1(2H)-one (3af)
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S11
Yellow solid; mp. 159–161 °C; IR (neat) 698, 756, 1508, 1636, 1645, 1653 cm-1; 1H NMR (400 MHz, CDCl3) ! 4.52 (2H, brs), 4.60 (1H, t, J = 7.2 Hz), 6.72 (2H, brs), 6.90-6.97 (4H, m), 7.13-7.20 (6H, m), 7.36 (2H, dd, J = 7.2, 8.0 Hz), 7.44 (1H, tt, J = 1.2, 7.6 Hz), 7.57 (1H, ddd, J = 1.2, 6.8, 8.0 Hz), 7.75 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 7.95 (1H, d, J = 8.0 Hz), 8.50 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 48.0, 52.0, 102.6, 125.6, 126.5, 126.6, 127.6, 128.2, 128.35, 128.43, 128.5, 129.1, 129.8, 133.1, 135.4, 135.6, 141.2, 142.3, 162.2; ESIHRMS: Found: m/z 480.0963. Calcd for C29H23NO 79Br: (M+H)+ 480.0963. 4-Bromo-2-pentyl-3-phenylisoquinolin-1(2H)-one (3ag)
Yellow oil; IR (neat) 762, 1092, 1339, 1474, 1582, 1647, 2930, 2955 cm-1; 1H NMR (400 MHz, CDCl3) ! 0.77 (3H, t, J = 6.8 Hz), 1.02-1.17 (4H, m), 1.56 (2H, tt, J = 7.2, 8.0 Hz), 3.79 (2H, t, J = 8.0 Hz), 7.33-7.37 (2H, m), 7.50-7.56 (3H, m), 7.57 (1H, ddd, J = 0.8, 7.2, 8.0 Hz), 7.75 (1H, ddd, J = 1.6, 7.2, 8.4 Hz), 7.98 (1H, d, J = 8.4 Hz), 8.50 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 13.8, 21.9, 28.3, 28.8, 47.4, 102.3, 125.7, 126.4, 127.5, 128.2, 128.7, 129.25, 129.28, 133.0, 135.4, 136.2, 142.2, 161.6; ESIHRMS: Found: m/z 370.0814. Calcd for C20H21NO 79Br: (M+H)+ 370.0807. 4-Bromo-2-(2-(cyclohex-1-en-1-yl)ethyl)-3-phenylisoquinolin-1(2H)-one (3ah)
White solid; mp. 107–109 °C; IR (neat) 752, 1578, 1609, 1636, 1647, 2859, 2924 cm-1; 1H NMR (400 MHz, CDCl3) ! 1.40-1.52 (4H, m), 1.66 (2H, brs), 1.85 (2H, brs), 2.15 (2H, t, J = 8.0 Hz), 3.86 (2H, t, J = 8.0 Hz), 5.21 (1H, brs), 7.34-7.38 (2H, m), 7.51-7.58 (4H, m), 7.74 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 7.97 (1H, d, J = 8.0 Hz), 8.49 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 22.1, 22.7, 25.1, 27.8, 36.9, 46.5, 102.3, 123.4, 125.6, 126.4, 127.5, 128.1, 128.7, 129.27, 129.34, 133.0, 134.1, 135.3, 136.0, 142.0, 161.6; ESIHRMS: Found: m/z 408.0964. Calcd for C23H23NO 79Br: (M+H)+ 408.0963. 4-Bromo-2-(cyclohexylmethyl)-3-phenylisoquinolin-1(2H)-one (3ai)
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S12
Mixture Rotational isomer (1.00 : 0.22) at room temperature; White solid; mp. 140–145 °C; IR (neat) 1335, 1506, 1578, 1645, 1717, 2849, 2926 cm-1; 1H NMR (400 MHz, CDCl3, the major isomer’s spectra was shown) ! 0.73-0.84 (2H, m), 1.01-1.12 (3H, m), 1.37-1.43 (2H, m), 1.52-1.70 (4H, m), 3.78 (2H, brs), 7.30-7.36 (2H, m), 7.48-7.55 (3H, m), 7.57 (1H, ddd, J = 1.2, 6.8, 8.0 Hz), 7.75 (1H, ddd, J = 1.6, 7.2, 8.4 Hz), 7.99 (1H, d, J = 8.0 Hz), 8.50 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3, the major isomer’s spectra was shown) ! 25.8, 26.1, 30.7, 37.5, 52.6, 102.6, 125.6, 126.4, 127.5, 128.3, 128.5, 129.1, 129.9, 133.0, 135.4, 136.0, 142.4, 162.1; ESIHRMS: Found: m/z 396.0956. Calcd for C22H23NO 79Br: (M+H)+ 396.0963. 4-Bromo-2-(cyclopropylmethyl)-3-phenylisoquinolin-1(2H)-one (3aj)
Orange solid; mp. 102–104 °C; IR (neat) 694, 764, 1474, 1607, 1645, 2851, 2924 cm-1; 1H NMR (400 MHz, CDCl3) ! 0.16-0.22 (2H, m), 0.33-0.38 (2H, m), 0.92-1.03 (1H, m), 3.82 (2H, d, J = 6.8 Hz), 7.33-7.40 (2H, m), 7.48-7.56 (3H, m), 7.55 (1H, t, J = 7.2 Hz), 7.74 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 7.97 (1H, d, J = 8.0 Hz), 8.50 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 4.2, 10.7, 50.8, 102.4, 125.7, 126.4, 127.5, 128.2, 128.6, 129.2, 129.7, 133.0, 135.4, 136.2, 142.0, 162.1; ESIHRMS: Found: m/z 354.0498. Calcd for C19H17NO 79Br: (M+H)+ 354.0494. 4-Bromo-2-(2-methoxyethyl)-3-phenylisoquinolin-1(2H)-one (3ak)
Yellow oil; IR (neat) 692, 760, 1103, 1115, 1580, 1647, 3003 cm-1; 1H NMR (400 MHz, CDCl3) ! 3.18 (3H, s), 3.54 (2H, t, J = 6.0 Hz), 4.06 (2H, t, J = 6.0 Hz), 7.32-7.37 (2H, m), 7.50-7.55 (3H, m), 7.57 (1H, ddd, J = 1.2, 7.2, 8.0 Hz), 7.77 (1H, ddd, J = 1.2, 7.2, 8.0 Hz), 7.99 (1H, d, J = 8.0 Hz), 8.49 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 46.4, 58.7, 69.4, 102.6, 125.5, 126.5, 127.6, 128.1, 128.7, 129.3, 129.7, 133.2, 135.6, 136.1, 142.4, 161.9; ESIHRMS: Found: m/z 358.0445. Calcd for C18H17NO2 79Br: (M+H)+ 358.0443. 4-Bromo-2-methyl-3-phenylisoquinolin-1(2H)-one (3al)
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S13
White solid; mp. 132–134 °C; IR (neat) 745, 756, 1117, 1339, 1474, 1636, 1645 cm-1; 1H NMR (400 MHz, CDCl3) ! 3.32 (3H, s), 7.31-7.35 (2H, m), 7.50-7.59 (4H, m), 7.75 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 7.98 (1H, d, J = 8.4 Hz), 8.50 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 35.1, 101.9, 125.3, 126.4, 127.6, 128.1, 128.98, 129.03, 129.3, 133.0, 135.4, 136.4, 142.2, 162.2; ESIHRMS: Found: m/z 314.0178. Calcd for C16H13NO 79Br: (M+H)+ 314.0181.
2-Methyl-3-phenylisoquinolin-1(2H)-one (4al)13
White solid; 1H NMR (400 MHz, CDCl3) ! 3.43 (3H, s), 6.46 (1H, s), 7.39-7.43 (2H, m), 7.45-7.51 (6H, m), 7.63 (1H, dd, J = 7.2, 7.6 Hz), 8.46 (1H, d, J = 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 34.1, 107.5, 124.9, 125.8, 126.6, 127.8, 128.6, 128.7, 128.9, 132.2, 136.2, 136.3, 143.9, 163.3.
–Table 3– 2-Benzyl-4-bromo-3-(4-methoxyphenyl)isoquinolin-1(2H)-one (3ba)
Sticky yellow oil; IR (neat) 750, 1032, 1173, 1248, 1508, 1609, 1645 cm-1; 1H NMR (400 MHz, CDCl3) ! 3.85 (3H, s), 5.18 (2H, brs), 6.84-6.90 (4H, m), 6.99 (2H, d, J = 8.4 Hz), 7.15-7.20 (3H, m), 7.59 (1H, ddd, J = 1.2, 7.2, 8.0 Hz), 7.78 (1H, ddd, J = 1.2, 7.2, 8.0 Hz), 8.01 (1H, d, J = 8.0 Hz), 8.55 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 50.0, 55.3, 103.5, 113.8, 125.5, 126.6, 126.7, 127.0, 127.7, 128.1, 128.2, 128.6, 130.8, 133.3, 135.6, 137.3, 142.2, 160.0, 162.3; ESIHRMS: Found: m/z 420.0605. Calcd for C23H19NO2 79Br: (M+H)+ 420.0599. 2-Benzyl-4-bromo-3-(4-methylphenyl)isoquinolin-1(2H)-one (3ca)
13 A. Couture, H. Cornet, P. Grandclaudon, J. Organomet. Chem. 1992, 440, 7.
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Sticky yellow oil; IR (neat) 1456, 1474, 1508, 1582, 1607, 1647, 3010 cm-1; 1H NMR (400 MHz, CDCl3) ! 2.40 (3H, s), 5.16 (2H, brs), 6.84-6.89 (2H, m), 6.97 (2H, d, J = 8.0 Hz), 7.14-7.19 (3H, m), 7.56 (1H, ddd, J = 1.2, 7.2, 8.0 Hz), 7.77 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.01 (1H, d, J = 8.0 Hz), 8.54 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 21.4, 50.0, 102.9, 125.5, 126.5, 126.7, 127.0, 127.6, 128.2, 128.5, 129.1, 129.3, 132.8, 133.2, 135.6, 137.2, 139.2, 142.4, 162.2; ESIHRMS: Found: m/z 404.0656. Calcd for C23H19NO 79Br: (M+H)+ 404.0650. 2-Benzyl-4-bromo-3-(4-fluorophenyl)isoquinolin-1(2H)-one (3da)
White solid; mp. 131–133 °C; IR (neat) 1223, 1238, 1373, 1506, 1636, 1717, 1734 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.17 (2H, brs), 6.80-6.85 (2H, m), 7.00-7.08 (4H, m), 7.16-7.20 (3H, m), 7.61 (1H, ddd, J = 1.2, 7.2, 8.0 Hz), 7.80 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.01 (1H, d, J = 8.0 Hz), 8.56 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 49.9, 103.3, 115.6 (d, J = 21.7 Hz), 125.6, 126.59, 126.62, 127.2, 127.9, 128.3, 128.6, 131.5 (d, J = 8.4 Hz), 131.6 (d, J = 3.8 Hz), 133.4, 135.4, 137.0, 141.2, 162.1, 162.9 (d, J = 248.6 Hz); ESIHRMS: Found: m/z 408.0392. Calcd for C22H16NOF 79Br: (M+H)+ 408.0399. Ethyl 4-(2-benzyl-4-bromo-1-oxo-1,2-dihydroisoquinolin-3-yl)benzoate (3ea)
Yellow oil; IR (neat) 760, 1022, 1099, 1271, 1506, 1653, 1717 cm-1; 1H NMR (400 MHz, CDCl3) ! 1.42 (3H, t, J = 7.2 Hz), 4.42 (2H, q, J = 7.2 Hz), 5.15 (2H, brs), 6.78-6.83 (2H, m), 7.12-7.20 (5H, m), 7.62 (1H, ddd, J = 0.8, 7.2, 8.0 Hz), 7.80 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.01 (1H, d, J = 8.0 Hz), 8.04 (2H, d, J = 8.4 Hz), 8.57 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 14.3, 49.9, 61.3, 102.6, 125.6, 126.6 (overlapped), 127.2, 128.1, 128.4, 128.6, 129.6, 129.7, 131.2, 133.4, 135.4, 136.8, 139.7, 141.2, 162.1, 165.8; ESIHRMS: Found: m/z 462.0703. Calcd for C25H21NO3 79Br: (M+H)+ 462.0705. 2-Benzyl-4-bromo-3-(4-trifluoromethylphenyl)isoquinolin-1(2H)-one (3fa)
Yellow oil; IR (neat) 760, 1067, 1128, 1167, 1321, 1647 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.14 (2H, brs), 6.75-6.81 (2H, m), 7.13-7.20 (5H, m), 7.59-7.66 (3H, m), 7.80 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.01 (1H, d, J = 8.0 Hz), 8.57 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 49.9,
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102.8, 123.7 (q, J = 270.6 Hz), 125.4 (q, J = 3.7 Hz), 125.7, 126.56, 126.63, 127.3, 128.2, 128.4, 128.7, 130.1, 131.3 (q, J = 32.6 Hz), 133.5, 135.3, 136.8, 139.0, 140.6, 162.1; ESIHRMS: Found: m/z 458.0359. Calcd for C23H16NOF3 79Br: (M+H)+ 458.0367. 2-Benzyl-4-bromo-3-(3-methoxyphenyl)isoquinolin-1(2H)-one (3ga)
Sticky oil; IR (neat) 1040, 1215, 1261, 1456, 1489, 1578, 1651 cm-1; 1H NMR (400 MHz, CDCl3) ! 3.56 (3H, s), 4.94 (1H, brd, J = 14.8 Hz), 5.38 (1H, brd. J = 15.2 Hz), 6.46 (1H, s), 6.73 (1H, d, J = 7.6 Hz), 6.83-6.90 (2H, m), 6.96 (1H, ddd, J = 0.8, 2.4, 8.4 Hz), 7.16-7.21 (3H, m), 7.31 (1H, t, J = 8.0 Hz), 7.60 (1H, ddd, J = 1.2, 7.6, 8.4 Hz), 7.79 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.02 (1H, d, J = 8.0 Hz), 8.56 (1H, dd, J = 1.2, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 50.0, 55.0, 102.6, 114.3, 115.7, 121.5, 125.5, 126.5, 126.7, 127.0, 127.7, 128.3, 128.5, 129.6, 133.3, 135.6, 136.6, 137.4, 142.0, 159.2, 162.2; ESIHRMS: Found: m/z 420.0602. Calcd for C23H19NO2 79Br: (M+H)+ 420.0599. 2-Benzyl-4-bromo-3-(2-methoxyphenyl)isoquinolin-1(2H)-one (3ha)
Yellow solid; mp. 108–110 °C; IR (neat) 758, 1256, 1495, 1578, 1599, 1636, 2965 cm-1; 1H NMR (400 MHz, CDCl3) ! 3.55 (3H, s), 4.93 (1H, brd, J = 15.2 Hz), 5.33 (1H, brd. J = 15.2 Hz), 6.82-6.88 (2H, m), 6.88-6.95 (3H, m), 7.11-7.16 (3H, m), 7.40-7.46 (1H, m), 7.58 (1H, ddd, J = 1.2, 7.6, 8.4 Hz), 7.77 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.00 (1H, d, J = 8.0 Hz), 8.56 (1H, dd, J = 1.2, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 49.8, 55.2, 103.3, 110.9, 120.4, 124.5, 125.6, 126.4, 126.9, 127.1, 127.5, 128.0, 128.5, 131.1, 131.3, 133.1, 135.7, 137.2, 139.7, 156.5, 162.4; ESIHRMS: Found: m/z 420.0598. Calcd for C23H19NO2 79Br: (M+H)+ 420.0599. 2-Benzyl-4-bromo-3-(2-bromophenyl)isoquinolin-1(2H)-one (3ia)
Yellow oil; IR (neat) 692, 752, 1026, 1327, 1472, 1607, 1647 cm-1; 1H NMR (400 MHz, CDCl3) ! 4.49 (1H, d, J = 15.2 Hz), 5.80 (1H, d, J = 15.6 Hz), 6.80-6.87 (3H, m), 7.11-7.20 (4H, m), 7.30 (1H, dt, J = 1.6, 8.0 Hz), 7.62 (1H, ddd, J = 1.2, 7.6, 8.4 Hz), 7.69 (1H, dd, J = 1.2, 8.0 Hz), 7.79 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.01 (1H, d, J = 8.0 Hz), 8.59 (1H, dd, J = 1.2, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 49.7, 103.4, 123.9, 125.8, 126.6, 127.0, 127.18, 127.22, 128.1, 128.2, 128.6,
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130.9, 132.1, 132.7, 133.3, 135.4, 136.4, 136.9, 140.8, 162.2; ESIHRMS: Found: m/z 469.9583. Calcd for C22H16NO 79Br 81Br: (M+H)+ 469.9578. 2-Benzyl-4-bromo-3-(2-naphthyl)isoquinolin-1(2H)-one (3ja)
Yellow oil; IR (neat) 748, 1337, 1506, 1582, 1647 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.02 (1H, brd, J = 15.2 Hz), 5.33 (1H, brd, J = 15.2 Hz), 6.77 (2H, d, J = 6.8 Hz), 7.07-7.20 (4H, m), 7.48-7.59 (3H, m), 7.62 (1H, ddd, J = 0.8, 7.2, 8.0 Hz), 7.68 (1H, d, J = 8.0 Hz), 7.80 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 7.85 (1H, d, J = 8.4 Hz), 7.89 (1H, d, J = 8.0 Hz), 8.03 (1H, d, J = 8.4 Hz), 8.59 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 50.1, 103.1, 125.6, 126.4, 126.57, 126.62, 126.8, 127.07, 127.13, 127.76, 127.81, 128.22, 128.24, 128.4, 128.6, 129.4, 132.6, 132.8, 133.1, 133.3, 135.6, 137.2, 142.1, 162.2; ESIHRMS: Found: m/z 440.0654. Calcd for C26H19NO 79Br: (M+H)+ 440.0650. 2-Benzyl-4-bromo-3-pentylisoquinolin-1(2H)-one (3ka)
N
O
Ph
n-C5H11Br
X-ray of 3ka
Colorless crystal; mp. 109–111 °C; IR (neat) 764, 1456, 1506, 1558, 1645, 1717 cm-1; 1H NMR (400 MHz, CDCl3) ! 0.91 (3H, t, J = 6.8 Hz), 1.30-1.42 (4H, m), 1.56-1.64 (2H, m), 2.90 (2H, t, J = 8.0 Hz), 5.50 (2H, brs), 7.14 (2H, d, J = 7.2 Hz), 7.25 (1H, t, J = 7.2 Hz), 7.31 (2H, dd, J = 6.8, 7.6 Hz), 7.51 (1H, ddd, J = 1.2, 7.2, 8.0 Hz), 7.74 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 7.98 (1H, d, J = 8.4 Hz), 8.46 (1H, dd, J = 1.2, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 13.9, 22.2, 27.9, 31.7, 33.6, 48.1, 102.3, 124.6, 125.9, 126.1, 127.0, 127.3, 128.5, 128.8, 133.2, 135.8, 137.0, 142.4, 162.5; ESIHRMS: Found: m/z 384.0969. Calcd for C21H23NO 79Br: (M+H)+ 384.0963. 2-Benzyl-4-bromo-3-cyclohexylisoquinolin-1(2H)-one (3la)
White solid; mp. 126–128 °C; IR (neat) 1339, 1456, 1506, 1576, 1607, 1636, 1653cm-1; 1H NMR (400 MHz, CDCl3) ! 0.92-1.50 (4H, m), 1.55-1.90 (4H, m), 2.53 (2H, dtd, J = 3.6, 12.4, 12.8 Hz), 3.06 (1H, tt, J = 3.2, 12.0 Hz), 5.57 (2H, brs), 7.19 (2H, d, J = 7.2 Hz), 7.23-7.28 (1H, m), 7.32 (2H, dd, J = 7.2, 7.6 Hz), 7.51 (1H, ddd, J = 1.2, 7.2, 8.0 Hz), 7.72 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.06
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(1H, d, J = 8.0 Hz), 8.47 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 25.4, 26.8, 27.9, 43.1, 48.6, 101.9, 124.6, 125.8, 126.2, 127.2, 127.3, 128.4, 128.7, 133.0, 136.2, 137.6, 145.2, 163.0; ESIHRMS: Found: m/z 396.0961. Calcd for C22H23NO 79Br: (M+H)+ 396.0963. 2-Benzyl-4-bromo-3-cyclopropylisoquinolin-1(2H)-one (3ma)
White solid; mp. 120–122 °C; IR (neat) 696, 764, 1456, 1506, 1576, 1645, 1717 cm-1; 1H NMR (400 MHz, CDCl3) ! 0.95-1.00 (2H, m), 1.23-1.29 (2H, m), 1.65 (1H, tt, J = 6.0, 8.4 Hz), 5.81 (2H, brs), 7.14 (2H, d, J = 7.2 Hz), 7.20-7.30 (3H, m), 7.52 (1H, ddd, J = 0.8, 7.2, 8.0 Hz), 7.73 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 8.02 (1H, d, J = 8.4 Hz), 8.46 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 12.1, 15.3, 47.5, 105.5, 125.1, 126.0, 126.3, 127.0, 127.3, 128.3, 128.6, 133.0, 135.8, 137.6, 141.3, 162.5; ESIHRMS: Found: m/z 354.0497. Calcd for C19H17NO 79Br: (M+H)+ 354.0494. 2-Benzyl-4-bromo-5-methyl-3-phenylisoquinolin-1(2H)-one (3na)
Yellow solid; mp. 141–143 °C; IR (neat) 694, 760, 1327, 1456, 1506, 1578, 1639 cm-1; 1H NMR (400 MHz, CDCl3) ! 2.96 (3H, s), 5.11 (2H, brs), 6.78-6.84 (2H, m), 7.04 (2H, d, J = 7.2 Hz), 7.13-7.18 (3H, m), 7.32-7.42 (3H, m), 7.45 (1H, dd, J = 7.6, 8.0 Hz), 7.57 (1H, d, J = 7.2 Hz), 8.54 (1H, d, J = 8.0 Hz) ; 13C NMR (100 MHz, CDCl3) ! 25.6, 50.2, 100.1, 126.8, 127.0, 127.30, 127.33, 127.6, 128.2, 128.5, 128.9, 129.5, 134.2, 135.3, 136.7, 137.1, 137.5, 142.7, 162.3; ESIHRMS: Found: m/z 404.0647. Calcd for C23H19NO 79Br: (M+H)+ 404.0650. 6-Benzyl-8-bromo-7-phenyl-[1,3]dioxolo[4,5-g]isoquinolin-5(6H)-one (3oa)
Sticky yellow oil; IR (neat) 696, 1036, 1231, 1406, 1472, 1568, 1645 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.13 (2H, brs), 6.14 (2H, s), 6.79-6.85 (2H, m), 7.05 (2H, d, J = 6.8 Hz), 7.14-7.19 (3H, m), 7.35 (2H, dd, J = 6.8, 8.0 Hz), 7.42 (1H, s), 7.42 (1H, tt, J = 1.2, 8.0 Hz), 7.90 (1H, s); 13C NMR (100 MHz, CDCl3) ! 50.0, 102.1, 102.4, 105.1, 106.3, 121.2, 126.7, 127.0, 128.2, 128.4, 129.1, 129.5, 133.2, 135.8, 137.2, 141.0, 148.4, 152.8, 161.3; ESIHRMS: Found: m/z 434.0389. Calcd for C23H17NO3 79Br: (M+H)+ 434.0392.
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2-Benzyl-4-bromo-7-methoxy-3-phenylisoquinolin-1(2H)-one (3pa)
Yellow solid; mp. 161–163 °C; IR (neat) 698, 939, 1038, 1406, 1474, 1645 cm-1; 1H NMR (400 MHz, CDCl3) ! 3.97 (3H, s), 5.16 (2H, brs), 6.80-6.87 (2H, m), 7.07 (2H, d, J = 7.2 Hz), 7.14-7.19 (3H, m), 7.32-7.39 (3H, m), 7.42 (1H, t, J = 7.2 Hz), 7.94 (1H, d, J = 9.2 Hz), 7.96 (1H, d, J = 2.4 Hz); 13C NMR (100 MHz, CDCl3) ! 50.1, 55.8, 102.7, 108.4, 123.6, 126.7, 127.0, 128.2, 128.37, 128.40 (overlapped), 129.1, 129.6, 129.8, 135.7, 137.2, 139.7, 159.4, 161.9; ESIHRMS: Found: m/z 420.0599. Calcd for C23H19NO2 79Br: (M+H)+ 420.0599. 2-Benzyl-4-bromo-7-fluoro-3-phenylisoquinolin-1(2H)-one (3qa)
Yellow solid; mp. 104–106 °C; IR (neat) 696, 752, 941, 1341, 1489, 1585, 1647 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.15 (2H, brs), 6.79-6.85 (2H, m), 7.06 (2H, d, J = 6.8 Hz), 7.14-7.20 (3H, m), 7.37 (2H, dd, J = 7.2, 8.0 Hz), 7.44 (1H, tt, J = 1.2, 7.2 Hz), 7.51 (1H, ddd, J = 2.8, 8.0, 8.8 Hz), 8.04 (1H, dd, J = 4.8, 8.8 Hz), 8.21 (1H, d, J = 1.2, 9.2 Hz); 13C NMR (100 MHz, CDCl3) ! 50.2, 102.1, 113.7 (d, J = 23.2 Hz), 121.8 (d, J = 23.4 Hz), 126.8, 127.1 (d, J = 7.8 Hz), 127.2, 128.3, 128.5, 129.3, 129.4 (d, J = 8.2 Hz), 129.5, 132.2 (d, J = 2.2 Hz), 135.4, 136.9, 141.5 (d, J = 2.8 Hz), 161.4 (d, J = 4.2 Hz), 162.0 (d, J = 247.9 Hz); ESIHRMS: Found: m/z 408.0405. Calcd for C22H16NOF 79Br: (M+H)+ 408.0399. 2-benzyl-4-bromo-3-phenylbenzofuro[2,3-c]pyridin-1(2H)-one (3ra)
White solid; mp. 182–184 °C; IR (neat) 743, 1038, 1456, 1474, 1647, 1668 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.28 (2H, brs), 6.79-6.85 (2H, m), 7.05 (2H, d, J = 7.2 Hz), 7.13-7.19 (3H, m), 7.39 (2H, t, J = 7.6 Hz), 7.42-7.49 (2H, m), 7.62 (1H, ddd, J = 1.2, 7.2, 8.4 Hz), 7.75 (1H, d, J = 8.8 Hz), 8.45 (1H, dd, J = 0.4, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 50.0, 95.5, 112.8, 123.4, 123.5, 123.6, 127.0, 127.3, 128.29, 128.32, 128.6, 129.3, 129.5, 129.8, 134.4, 136.7, 142.7, 143.3, 154.1, 156.9; ESIHRMS: Found: m/z 430.0437. Calcd for C24H17NO2 79Br: (M+H)+ 430.0443. 6-Benzyl-8-bromo-7-phenyl-1,6-naphthyridin-5(6H)-one (3sa)
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Yellow solid; mp. 138–140 °C; IR (neat) 698, 1435, 1456, 1541, 1558, 1638 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.17 (2H, brs), 6.80-6.87 (2H, m), 7.10 (2H, d, J = 7.2 Hz), 7.15-7.21 (3H, m), 7.39 (2H, dd, J = 6.8, 7.6 Hz), 7.46 (1H, tt, J = 1.2, 7.2 Hz), 7.54 (1H, dd, J = 4.8, 8.0 Hz), 8.81 (1H, dd, J = 1.6, 8.0 Hz), 9.09 (1H, dd, J = 1.6, 4.8 Hz); 13C NMR (100 MHz, CDCl3) ! 50.0, 104.7, 121.4, 122.6, 126.7, 127.2, 128.3, 128.5, 129.0, 129.4, 135.0, 136.6, 137.1, 146.2, 150.2, 155.1, 162.1; ESIHRMS: Found: m/z 391.0443. Calcd for C21H16N2O 79Br: (M+H)+ 391.0446.
6-Benzyl-7-phenyl-1,6-naphthyridin-5(6H)-one (4sa)
Yellow solid; mp. 113–115 °C; IR (neat) 704, 839, 1358, 1437, 1506, 1558, 1653 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.24 (2H, brs), 6.72 (1H, s), 6.87-6.93 (2H, m), 7.15-7.20 (3H, m), 7.23 (2H, d, J = 7.2 Hz), 7.36 (2H, dd, J = 7.2, 8.0 Hz), 7.41-7.46 (2H, m), 8.74 (1H, dd, J = 1.2, 8.0 Hz), 8.93 (1H, dd, J = 1.6, 4.8 Hz); 13C NMR (100 MHz, CDCl3) ! 48.6, 109.8, 120.9, 121.7, 126.8, 127.1, 128.3 (overlapped), 128.8, 129.2, 135.2, 136.6, 137.1, 147.8, 152.9, 154.8, 163.1; ESIHRMS: Found: m/z 313.1335. Calcd for C21H17N2O: (M+H)+ 313.1341.
3.2. The reactions with CuCl and CuI It was found that CuCl and CuI also showed the reactivity in the present reaction conditions, giving 4-chloro- and 4-iodoisoquinolones 3aa’ and 3aa”, respectively, while lower yields were observed.
Scheme S1.
+N
O
Ph
PhX
3aa' (X = Cl); 23%3aa" (X = l); 39%**
1a(0.5 mmol)
2a(3 equiv)
CuX(2.2 equiv)
benzene-pyridine(5 : 1)
SiO2, 80 °Cunder O2 (1 atm)
**Pydirine was used as a sole solvent.
2-Benzyl-4-chloro-3-phenylisoquinolin-1(2H)-one (3aa’)
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Synthesized from 2.2 equiv of CuCl; Yellow oil; IR (neat) 696, 752, 1477, 1495, 1585, 1611, 1647 cm-1; 1H NMR (400 MHz, CDCl3) ! 5.15 (2H, brs), 6.80-6.86 (2H, m), 7.09 (2H, d, J = 6.8 Hz), 7.14-7.18 (3H, m), 7.36 (2H, dd, J = 6.8, 7.6 Hz), 7.43 (1H, t, J = 7.6 Hz), 7.61 (1H, dt, J = 0.8, 7.6 Hz), 7.79 (1H, dt, J = 1.2, 7.6 Hz), 8.00 (1H, d, J = 8.0 Hz), 8.57 (1H, dd, J = 0.8, 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 49.5, 111.8, 123.8, 125.5, 126.8, 127.1, 127.8, 128.3, 128.5, 128.6,129.2, 129.6, 133.1, 133.6, 134.7, 137.2, 140.5, 162.0; ESIHRMS: Found: m/z 346.1003. Calcd for C22H17NOCl: (M+H)+ 346.0999. 2-Benzyl-4-iodo-3-phenylisoquinolin-1(2H)-one (3aa’’)
Synthesized from 2.2 equiv of CuI in pyridine (0.1 M); White solid; IR (neat) 696, 762, 1030, 1339, 1587, 1603, 1647 cm-1; mp. 86–88 °C; 1H NMR (400 MHz, CDCl3) ! 5.20 (2H, brs), 6.80-6.86 (2H, m), 7.02 (2H, d, J = 7.6 Hz), 7.14-7.18 (3H, m), 7.35 (2H, dd, J = 7.2, 7.6 Hz), 7.42 (1H, t, J = 7.2 Hz), 7.57 (1H, t, J = 7.6 Hz), 7.75 (1H, t, J = 7.6 Hz), 7.96 (1H, d, J = 8.0 Hz), 8.51 (1H, d, J = 8.0 Hz); 13C NMR (100 MHz, CDCl3) ! 50.8, 79.9, 125.2, 126.7, 127.0, 127.8, 128.2, 128.4, 128.6, 129.3, 129.5, 131.7, 133.6, 137.2, 137.4, 139.3, 145.7, 162.5; ESIHRMS: Found: m/z 438.0354. Calcd for C22H17NOI: (M+H)+ 438.0355.
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3.3. The reactions with !-alanine ethyl ester (2m) and propargylamine 2n The reaction of !-alanine ethyl ester (2m) (as a hydrochloride salt) with 1a under the standard reaction conditions provided 4-bromoisoquinoline 5 and protonated isoquinoline 6 in 42% and 28% yields, respectively, with certain C-N bond cleavage, and no desired 4-bromoisoquinolone was formed at all (Scheme S2). Similarly, 3-phenylprop-2-yn-1-amine (2n) also delivered 4-bromoisoquinoline 5 without forming 4-bromoisoquinolone 3. It is noted that aromatic amines (anilines) did not work at all to provide any cyclized product under the present reaction conditions.
Scheme S2.
O
H
Ph
H2N
CuBr•SMe2(2.2 equiv)
benzene-pyridine(5 : 1)
SiO2, 80 °Cunder O2 (1 atm)
2 h
N
XPh
+
1a(0.5 mmol)
2m(1.2 equiv)
5 (X = Br); 42%6 (X = H); 28%
CO2EtCl–
O
H
Ph
H2N
CuBr•SMe2(2.2 equiv)
benzene-pyridine(5 : 1)
SiO2, 80 °Cunder O2 (1 atm)
4 h
N
BrPh
+
1a(0.5 mmol)
2n(3 equiv)
5 30%
Ph
4-Bromo-3-phenylisoquinoline (5)14
White solid; 1H NMR (400 MHz, CDCl3) ! 7.41-7.53 (3H, m), 7.66 (1H, ddd, J = 0.8, 7.2, 8.0 Hz), 7.71-7.76 (2H, m), 7.82 (1H, ddd, J = 1.2, 6.8, 8.4 Hz), 7.98 (1H, d, J = 8.0 Hz), 8.31 (1H, dd, J = 0.8, 8.8 Hz), 9.22 (1H, s); 13C NMR (100 MHz, CDCl3) ! 118.2, 126.9, 127.7, 127.8, 127.9, 128.3, 128.5, 129.8, 131.8, 135.9, 140.7, 151.0, 152.3. 3-Phenylisoquinoline (6)15
White solid; 1H NMR (400 MHz, CDCl3) ! 7.41 (1H, tt, J = 1.2, 7.6 Hz), 7.48-7.53 (2H, m), 7.57 (1H, ddd, J = 1.2, 6.8, 8.0 Hz), 7.68 (1H, ddd, J = 1.2, 6.8, 8.0 Hz), 7.86 (1H, d, J = 8.0 Hz), 7.97
14 H.-P. Zhang, S.-C. Yu, Y. Liang, P. Peng, B.-X. Tang, J.-H. Li, Synlett 2011, 982. 15 Y.-N. Niu, Z.-Y. Yan, G.-L. Gao, H.-L. Wang, X.-Z. Shu, K.-G. Ji, Y.-M. Liang, J. Org. Chem. 2009, 74, 2893.
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(1H, d, J = 8.0 Hz), 8.06 (1H, s), 8.10-8.15 (2H, m), 9.33 (1H, s); 13C NMR (100 MHz, CDCl3) ! 116.5, 126.8, 126.9, 127.0, 127.5, 127.7, 128.4, 128.7, 130.4, 136.5, 139.5, 151.2, 152.3. 4. Control experiments to elucidate the reaction mechanism To elucidate the reaction mechanism for the formation of 4-bromoisoquinolone derivatives 3, especially pertaining to how N-C bond forming cyclization as well as formation of C=O and C-Br bonds could occur, several control experiments were conducted (Scheme S3). The reaction of N-benzylaldimines 7 under the standard reaction conditions afforded 4-bromoisoquinolone 3aa (Scheme S3-a), while cyclization of N-benzylamide 8 did not proceed at all (Scheme S3-b). With the fact that the reaction of benzaldehyde (9) and benzylamine (2a) under the present conditions gave only aldimine 10 derived from condensation of 9 and 2a as well as dimerization of 2a (Scheme S3-c), it could be expected that the N-C bond forming cyclization onto alkyne might occur prior to the C=O bond formation. Stahl reported a CuBr-catalyzed aerobic bromination of arenes in the presence of LiBr as a stoichiometric bromine atom source, where molecular bromine generated in situ underwent an electrophilic bromination. 16 On the contrary, treatment of cyclooctene (11) under the present reaction conditions (2.2 equiv of CuBr•SMe2, SiO2, in benzene-pyridine under an O2 atmosphere) did not afford any electrophilic bromination product (Scheme S3-d). This suggested that molecular bromine (or a precursor of bromonium cation) is not likely involved in the present 4-bromoisoquinolone formation. It is also noted that vinylic C-H bromination of isoquinolone 4aa did not proceed under the present reaction conditions (Scheme S3-e).
Scheme S3.
N
Ph
PhN
O
PhBr
Ph(a)
NH
Ph
Ph
O
3aa 36%
no reaction(recovery of 8 in 81% yield)
(b)
H N Ph
O
+ H2N Ph
standardconditions
standardconditions
standardconditions
(c)
**standard conditions: CuBr•SMe2 (2.2 equiv) in benzene-pyridine (5:1), SiO2 80 °C, under an O2 atmosphere (1 atm).
7
8
9 2a (3 equiv) 10 116% based on 9
standardconditions Br
X0%11
(d)
N
O
PhBr
Ph
3aa 0%
standardconditionsN
O
PhH
Ph
4aa
(e)
16 L. Yang, Z. Lu and S. S. Stahl, Chem. Commun. 2009, 6460.
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Preparation of N-benzyl-2-(2-phenylethynyl)benzaldimine (7):
Ph
H
O
+ H2N PhMS 4A
CH2Cl2, rt24 h Ph
N Ph
1a2a
7 To a solution of 2-(2-phenylethynyl)benzaldehyde (1a) (206 mg, 1.0 mmol) in 1 mL of CH2Cl2 were added benzylamine (2a) (107 mg, 1.0 mmol) and MS 4Å (20 mg). The reaction mixture was allowed to stir at room temperature for 24 h. After the completion of reaction, the mixture was filtered and volatile materials were removed in vacuo and the crude material was used for next reaction without further purification. N-Benzyl-2-(2-phenylethynyl)benzaldimine (7)5 Brown oil; 1H NMR (400 MHz, CDCl3) ! 4.90 (2H, s), 7.36-7.40 (10H, m), 7.50-7.57 (3H, m), 8.14 (1H, d, J = 6.8 Hz), 8.99 (1H, s); 13C NMR (100 MHz, CDCl3) ! 65.1, 86.4, 94.9, 122.9, 124.1, 126.4, 127.0, 128.1, 128.4, 128.5, 128.58, 128.63, 130.3, 131.5, 132.5, 136.7, 139.1, 160.5. N-Benzyl-2-(phenylethynyl)benzamide (8)17
NH
O
Ph
Ph Prepared from N-benzyl-2-bromobenzamide and phenylacetylene by the same procedure with the section 2.1., and purified by flash column chromatography (Si gel, hexane:ethyl acetate = 80:20) in 95% yield; White solid; 1H NMR (400 MHz, CDCl3) ! 4.70 (2H, d, J = 5.6 Hz), 7.13 (2H, d, J = 7.2 Hz), 7.22-7.29 (5H, m), 7.30-7.40 (3H, m), 7.42-7.48 (2H, m), 7.56-7.61 (1H, m), 7.80 (1H, brs), 8.12-8.17 (1H, m); 13C NMR (100 MHz, CDCl3) ! 44.5, 87.5, 95.8, 119.6, 121.8, 127.5, 128.2, 128.4, 128.75, 128.86, 128.92, 130.2, 130.6, 131.4, 133.6, 135.0, 137.8, 166.1. Both imine 10 and isoquinolone 4aa were known compounds (see the references). N-Benzyl-benzaldimine (10)18
2-Benzyl-3-phenylisoquinolin-1(2H)-one (4aa)19
N
O
PhH
Ph
17 G. Liu, Y. Zhou, D. Ye, D. Zhang, X. Ding, H. Jiang, H. Liu, Adv. Synth. Catal. 2009, 351, 2605. 18 L. G. Marinescu, C. M. Pedersen, M. Bols, Tetrahedron 2004, 61, 123. 19 N. Sakai, K. Annaka, A. Fujita, A. Sato, T. Konakahara, J. Org. Chem. 2008, 73, 4160.
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4. 1H and 13C NMR spectrum of new compounds
S24
1H NMR spectrum of 1d (400 MHz, CDCl3)
11 10 9 8 7 6 5 4 3 2 1 ppm
7.062
7.067
7.079
7.084
7.089
7.101
7.106
7.263
7.442
7.461
7.477
7.479
7.480
7.535
7.540
7.548
7.552
7.557
7.566
7.570
7.586
7.589
7.604
7.607
7.624
7.626
7.643
7.646
7.939
7.941
7.958
7.960
10.623
10.624
2.06
1.05
3.15
1.03
1.03
1.00
7.17.27.37.47.57.67.77.87.98.0 ppm
7.06
27.
067
7.07
97.
084
7.08
97.
101
7.10
6
7.26
3
7.44
27.
461
7.47
77.
479
7.48
07.
535
7.54
07.
548
7.55
27.
557
7.56
67.
570
7.58
67.
589
7.60
47.
607
7.62
47.
626
7.64
37.
646
7.93
97.
941
7.95
87.
960
2.06
5
1.05
2
3.15
2
1.02
9
1.02
6
10.6010.65 ppm
10.6
2310
.624
1.00
0
!
H
O
F
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4. 1H and 13C NMR spectrum of new compounds
S25
13C NMR spectrum of 1d (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm76.68
77.00
77.32
84.65
95.16
115.77
115.99
118.40
118.43
126.59
127.37
128.66
133.15
133.59
133.68
133.78
135.78
161.66
164.16
191.54
!
H
O
F
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4. 1H and 13C NMR spectrum of new compounds
S26
1H NMR spectrum of 1j (400 MHz, CDCl3)
11 10 9 8 7 6 5 4 3 2 1 ppm
7.259
7.459
7.478
7.497
7.520
7.528
7.536
7.544
7.553
7.590
7.594
7.597
7.613
7.615
7.632
7.635
7.687
7.689
7.707
7.708
7.831
7.839
7.846
7.854
7.862
7.967
7.969
7.987
7.989
8.107
10.726
10.727
1.03
1.99
2.00
1.01
2.99
0.97
0.99
1.00
10.7210.74 ppm
10.7
2610
.727
1.00
0
6.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.4 ppm
7.25
9
7.45
97.
478
7.49
77.
520
7.52
87.
536
7.54
47.
553
7.59
07.
594
7.59
77.
613
7.61
57.
632
7.63
57.
687
7.68
97.
707
7.70
87.
831
7.83
97.
846
7.85
47.
862
7.96
77.
969
7.98
77.
989
8.10
7
1.03
3
1.98
9
2.00
0
1.01
0
2.99
0
0.97
0
0.99
0
!
H
O
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S27
13C NMR spectrum of 1j (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm76.68
77.00
77.32
85.20
96.75
119.54
126.76
126.86
127.09
127.30
127.80
127.87
128.03
128.24
128.61
131.87
132.89
133.10
133.22
133.79
135.84
191.69
!
H
O
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S28
1H NMR spectrum of 1n (400 MHz, CDCl3)
11 10 9 8 7 6 5 4 3 2 1 ppm
2.589
7.259
7.332
7.351
7.371
7.388
7.393
7.396
7.404
7.413
7.491
7.509
7.510
7.566
7.570
7.573
7.576
7.580
7.582
7.590
7.787
7.787
7.806
7.807
10.689
10.691
3.00
4.34
1.07
2.12
1.00
0.95
10.7 ppm
10.689
10.691
0.946
7.17.27.37.47.57.67.77.87.98.0 ppm
7.259
7.332
7.351
7.371
7.388
7.393
7.396
7.404
7.413
7.491
7.509
7.510
7.566
7.570
7.573
7.576
7.580
7.582
7.590
7.787
7.787
7.806
7.807
4.336
1.072
2.119
1.000
!
H
O
PhMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S29
13C NMR spectrum of 1n (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
20.48
76.68
77.00
77.32
83.61
100.81
122.55
124.65
126.61
128.06
128.52
128.98
131.53
134.84
135.99
141.54
192.25
!
H
O
PhMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S30
1H NMR spectrum of 1r (400 MHz, CDCl3)
11 10 9 8 7 6 5 4 3 2 1 ppm
7.260
7.402
7.405
7.411
7.414
7.422
7.425
7.436
7.440
7.452
7.552
7.555
7.574
7.577
7.590
7.593
7.603
7.628
7.635
7.639
7.647
7.652
7.883
7.903
10.126
4.19
4.36
1.07
1.00
10.1210.14 ppm
10.1
26
1.00
0
7.37.47.57.67.77.87.9 ppm
7.26
0
7.40
27.
405
7.41
17.
414
7.42
27.
425
7.43
67.
440
7.45
2
7.55
27.
555
7.57
47.
577
7.59
07.
593
7.60
37.
628
7.63
57.
639
7.64
77.
652
7.88
37.
903
4.19
3
4.35
8
1.07
3
!
H
O
Ph
O
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S31
13C NMR spectrum of 1r (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm76.68
77.00
77.32
100.07
112.83
115.87
121.78
122.55
124.52
127.48
128.61
129.59
130.01
131.93
152.48
155.37
178.01
!
H
O
Ph
O
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S32
1H NMR spectrum of 3aa (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
5.157
6.815
6.824
6.833
6.838
7.052
7.070
7.143
7.148
7.153
7.159
7.169
7.239
7.327
7.345
7.364
7.398
7.416
7.432
7.435
7.559
7.562
7.580
7.598
7.600
7.742
7.745
7.763
7.781
7.784
7.988
8.008
8.542
8.544
2.03
2.04
2.03
3.09
2.08
1.10
1.09
1.05
1.02
1.00
5.05.56.06.57.07.58.08.5 ppm
5.15
7
6.81
56.
824
6.83
36.
838
7.05
27.
070
7.14
37.
148
7.15
37.
159
7.16
97.
239
7.32
77.
345
7.36
47.
398
7.41
67.
432
7.43
57.
559
7.56
27.
580
7.59
87.
600
7.74
27.
745
7.76
37.
781
7.78
47.
988
8.00
8
8.54
28.
544
8.56
28.
564
2.03
3
2.04
0
2.03
03.
088
2.08
31.
104
1.08
7
1.04
6
1.02
0
1.00
0
!
N
O
Ph
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S33
13C NMR spectrum of 3aa (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
49.92
76.68
77.00
77.32
102.76
125.52
126.51
126.72
127.02
127.71
128.20
128.37
128.53
129.16
129.44
133.26
135.54
135.60
137.11
142.20
162.12
!
N
O
Ph
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S34
1H NMR spectrum of 3aa’ (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm5.146
6.820
6.829
6.838
6.843
7.080
7.097
7.150
7.152
7.155
7.160
7.166
7.176
7.252
7.345
7.362
7.381
7.412
7.415
7.418
7.433
7.449
7.452
7.590
7.592
7.610
7.628
7.630
7.775
7.778
7.796
7.798
7.813
7.817
7.993
1.98
2.03
2.03
3.06
2.29
1.19
1.09
1.16
1.04
1.00
5.05.56.06.57.07.58.08.59.0 ppm
5.14
6
6.82
06.
829
6.83
86.
843
7.08
07.
097
7.15
07.
152
7.15
57.
160
7.16
67.
176
7.25
27.
345
7.36
27.
381
7.41
27.
415
7.41
87.
433
7.44
97.
452
7.59
07.
592
7.61
07.
628
7.63
07.
775
7.77
87.
796
7.79
87.
813
7.81
77.
993
8.01
38.
558
8.56
08.
578
8.58
0
1.98
4
2.02
7
2.03
53.
063
2.29
11.
193
1.09
5
1.16
0
1.03
8
1.00
0
!
N
O
Ph
PhCl
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S35
13C NMR spectrum of 3aa’ (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
49.52
76.68
77.00
77.32
111.83
123.85
125.52
126.79
127.08
127.76
128.26
128.46
128.60
129.25
129.59
133.13
133.62
134.71
137.15
140.54
161.98
!
N
O
Ph
PhCl
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S36
1H NMR spectrum of 3aa’’ (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
5.198
6.812
6.821
6.830
7.007
7.025
7.150
7.159
7.164
7.250
7.333
7.352
7.370
7.404
7.422
7.440
7.547
7.565
7.585
7.729
7.747
7.749
7.768
7.945
7.966
8.500
8.520
2.08
2.07
2.05
3.08
2.15
1.02
1.11
1.06
1.04
1.00
5.56.06.57.07.58.08.5 ppm
5.19
8
6.81
26.
821
6.83
07.
007
7.02
57.
150
7.15
97.
164
7.25
07.
333
7.35
27.
370
7.40
47.
422
7.44
07.
547
7.56
57.
585
7.72
97.
747
7.74
97.
768
7.94
57.
966
8.50
08.
520
2.07
9
2.06
8
2.04
5
3.07
8
2.15
31.
020
1.10
7
1.06
2
1.03
6
1.00
0
!
N
O
Ph
PhI
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S37
13C NMR spectrum of 3aa’’ (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
50.79
76.68
77.00
77.32
79.88
125.22
126.71
127.04
127.77
128.23
128.41
128.60
129.26
129.52
131.71
133.60
137.22
137.43
139.27
145.70
162.53
!
N
O
Ph
PhI
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S38
1H NMR spectrum of 3ab (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm3.742
5.097
6.671
6.678
6.684
6.695
6.700
6.707
6.751
6.773
7.078
7.096
7.258
7.370
7.374
7.391
7.410
7.430
7.433
7.437
7.452
7.467
7.470
7.572
7.574
7.590
7.592
7.594
7.610
7.612
7.756
7.759
7.774
7.777
7.779
7.794
7.798
3.10
1.95
2.01
2.02
1.96
2.09
1.04
1.05
1.03
1.01
1.00
6.46.66.87.07.27.47.67.88.08.28.48.68.8 ppm
6.67
16.
678
6.68
46.
695
6.70
06.
707
6.75
16.
773
7.07
87.
096
7.25
87.
370
7.37
47.
391
7.41
07.
430
7.43
37.
437
7.45
27.
467
7.47
07.
572
7.57
47.
590
7.59
27.
594
7.61
07.
612
7.75
67.
759
7.77
47.
777
7.77
97.
794
7.79
87.
995
8.01
5
8.54
28.
545
8.56
38.
565
2.01
42.
019
1.96
2
2.08
61.
040
1.04
8
1.03
4
1.00
6
1.00
0
!
N
O
PhBr
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S39
13C NMR spectrum of 3ab (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
49.42
55.18
76.68
77.00
77.32
102.79
113.57
125.63
126.53
127.71
128.35
128.41
128.55
129.20
129.29
129.60
133.26
135.58
135.71
142.24
158.67
162.22
!
N
O
PhBr
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S40
1H NMR spectrum of 3ac (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
2.270
5.108
6.721
6.741
6.956
6.976
7.082
7.086
7.103
7.260
7.359
7.362
7.379
7.398
7.422
7.425
7.428
7.444
7.462
7.573
7.576
7.594
7.596
7.611
7.614
7.762
7.766
7.780
7.783
7.786
7.801
7.804
8.004
8.023
8.024
3.08
2.02
2.00
2.00
2.10
2.00
1.06
1.00
0.99
0.98
1.00
6.66.87.07.27.47.67.88.08.28.48.68.89.0 ppm
6.72
16.
741
6.95
66.
976
7.08
27.
086
7.10
37.
260
7.35
97.
362
7.37
97.
398
7.42
27.
425
7.42
87.
444
7.46
27.
573
7.57
67.
594
7.59
67.
611
7.61
47.
762
7.76
67.
780
7.78
37.
786
7.80
17.
804
8.00
48.
023
8.02
48.
539
8.54
18.
559
8.56
1
2.00
2
2.00
2
2.10
0
2.00
01.
063
0.99
8
0.99
4
0.97
8
1.00
0
!
N
O
PhBr
Me
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S41
13C NMR spectrum of 3ac (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
21.02
49.79
76.68
77.00
77.32
102.71
125.57
126.49
126.75
127.67
128.39
128.53
128.87
129.15
129.49
133.22
134.07
135.54
135.66
136.64
142.27
162.12
!
N
O
PhBr
Me
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S42
1H NMR spectrum of 3ad (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
5.127
6.780
6.785
6.794
6.802
6.809
6.815
6.823
6.830
6.835
6.846
6.851
6.857
6.868
6.873
7.061
7.079
7.260
7.369
7.372
7.389
7.409
7.434
7.438
7.441
7.456
7.472
7.475
7.478
7.589
7.591
7.607
7.609
7.627
7.630
7.774
7.778
7.793
7.795
7.798
2.01
4.07
2.00
2.09
1.10
1.05
1.05
1.02
1.00
6.66.87.07.27.47.67.88.08.28.48.6 ppm
6.78
06.
785
6.79
46.
802
6.80
96.
815
6.82
36.
830
6.83
56.
846
6.85
16.
857
6.86
86.
873
7.06
17.
079
7.26
07.
369
7.37
27.
389
7.40
97.
434
7.43
87.
441
7.45
67.
472
7.47
57.
478
7.58
97.
591
7.60
77.
609
7.62
77.
630
7.77
47.
778
7.79
37.
795
7.79
87.
813
7.81
68.
008
8.02
88.
029
8.54
18.
543
8.56
18.
564
4.06
9
1.99
6
2.08
91.
100
1.05
5
1.04
9
1.02
1
1.00
0
!
N
O
PhBr
F
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S43
13C NMR spectrum of 3ad (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
49.20
76.68
77.00
77.32
102.93
114.94
115.15
125.45
126.56
127.80
128.45
128.49
128.62
128.70
129.27
129.49
132.87
132.90
133.35
135.51
135.53
141.94
160.65
162.13
163.09
!
N
O
PhBr
F
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S44
1H NMR spectrum of 3ae (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
2.852
2.871
2.893
3.985
4.005
4.026
6.855
6.871
7.152
7.168
7.187
7.202
7.208
7.255
7.282
7.290
7.300
7.305
7.547
7.556
7.562
7.572
7.580
7.598
7.617
7.758
7.778
7.797
7.994
8.015
8.527
8.547
2.07
2.02
2.04
3.03
2.07
4.05
1.05
1.02
1.00
6.66.87.07.27.47.67.88.08.28.48.68.8 ppm
6.85
56.
871
7.15
27.
168
7.18
77.
202
7.20
87.
255
7.28
27.
290
7.30
07.
305
7.54
77.
556
7.56
27.
572
7.58
07.
598
7.61
77.
758
7.77
87.
797
7.99
48.
015
8.52
78.
547
2.04
5
3.03
2
2.07
4
4.05
0
1.05
5
1.02
0
1.00
0
!
N
O
PhBr
Ph
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S45
13C NMR spectrum of 3ae (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
34.71
49.06
76.68
77.00
77.32
102.44
125.61
126.44
126.48
127.70
128.11
128.43
128.71
128.84
129.32
129.40
133.16
135.43
135.98
138.08
141.97
161.67
!
N
O
PhBr
Ph
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S46
1H NMR spectrum of 3af (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
4.521
4.578
4.597
4.615
6.724
6.922
6.930
7.136
7.146
7.156
7.161
7.169
7.173
7.183
7.192
7.196
7.244
7.343
7.361
7.381
7.418
7.421
7.424
7.440
7.455
7.458
7.461
7.548
7.551
7.569
7.586
7.589
7.724
7.728
7.742
7.745
7.748
7.763
7.766
2.90
1.97
4.00
6.08
2.07
0.97
1.04
1.02
1.01
1.00
6.46.66.87.07.27.47.67.88.08.28.48.68.8 ppm
6.72
46.
922
6.93
07.
136
7.14
67.
156
7.16
17.
169
7.17
37.
183
7.19
27.
196
7.24
47.
343
7.36
17.
381
7.41
87.
421
7.42
47.
440
7.45
57.
458
7.46
17.
548
7.55
17.
569
7.58
67.
589
7.72
47.
728
7.74
27.
745
7.74
87.
763
7.76
67.
940
7.94
07.
960
8.49
18.
493
8.51
18.
513
1.97
5
4.00
3
6.08
0
2.07
30.
968
1.04
4
1.01
9
1.01
0
1.00
0
!
N
O
PhBr
Ph
Ph
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S47
13C NMR spectrum of 3af (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
48.04
52.05
76.68
77.00
77.32
102.61
125.57
126.55
126.64
127.63
128.21
128.35
128.43
128.52
129.06
129.82
133.15
135.44
135.59
141.20
142.28
162.21
!
N
O
PhBr
Ph
Ph
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S48
1H NMR spectrum of 3ag (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
0.753
0.771
0.788
1.041
1.048
1.060
1.079
1.086
1.098
1.101
1.117
1.135
1.537
1.555
1.576
1.595
1.617
2.174
3.773
3.793
3.813
7.262
7.331
7.336
7.343
7.348
7.355
7.511
7.517
7.523
7.527
7.535
7.537
7.539
7.541
7.546
7.549
7.553
7.560
7.564
7.567
7.569
7.585
7.587
7.732
7.735
7.750
7.753
7.756
7.770
7.774
7.970
7.971
7.991
3.10
4.09
2.16
2.09
2.07
4.11
1.06
1.03
1.00
7.07.27.47.67.88.08.28.48.6 ppm
7.26
27.
331
7.33
67.
343
7.34
87.
355
7.51
17.
517
7.52
37.
527
7.53
57.
537
7.53
97.
541
7.54
67.
549
7.55
37.
560
7.56
47.
567
7.56
97.
585
7.58
77.
732
7.73
57.
750
7.75
37.
756
7.77
07.
774
7.97
07.
971
7.99
1
8.48
78.
489
8.50
78.
509
2.07
1
4.11
4
1.06
2
1.02
7
1.00
0
!
N
O
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S49
13C NMR spectrum of 3ag (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
13.80
21.90
28.28
28.81
47.36
76.68
77.00
77.32
102.26
125.67
126.38
127.55
128.16
128.71
129.25
129.28
132.99
135.43
136.16
142.15
161.64
!
N
O
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S50
1H NMR spectrum of 3ah (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
0.000
1.425
1.432
1.438
1.447
1.451
1.463
1.478
1.482
1.494
1.497
1.506
1.520
1.620
1.659
1.839
2.131
2.151
2.172
3.843
3.863
3.884
5.210
7.261
7.349
7.353
7.361
7.366
7.372
7.523
7.530
7.534
7.541
7.548
7.557
7.566
7.584
7.586
7.730
7.733
7.751
7.769
7.772
7.970
7.991
8.482
8.484
8.502
8.504
4.17
2.06
2.04
2.05
1.97
0.99
2.11
4.20
1.07
1.01
1.00
7.07.27.47.67.88.08.28.48.68.8 ppm
7.26
17.
349
7.35
37.
361
7.36
67.
372
7.52
37.
530
7.53
47.
541
7.54
87.
557
7.56
67.
584
7.58
67.
730
7.73
37.
751
7.76
97.
772
7.97
07.
991
8.48
28.
484
8.50
28.
504
2.10
5
4.20
3
1.07
4
1.01
1
1.00
0
!
N
O
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S51
13C NMR spectrum of 3ah (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
22.10
22.75
25.12
27.82
36.94
46.60
76.68
77.00
77.32
102.31
123.48
125.69
126.41
127.59
128.13
128.73
129.32
129.39
133.01
134.12
135.42
136.05
142.09
161.63
!
N
O
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S52
1H NMR spectrum of 3ai (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
0.743
0.751
0.773
0.780
0.803
0.832
1.010
1.033
1.053
1.074
1.080
1.087
1.385
1.416
1.570
1.589
1.595
1.605
1.615
1.625
1.634
1.643
1.652
1.662
3.773
3.785
7.262
7.313
7.317
7.322
7.325
7.331
7.337
7.500
7.509
7.512
7.518
7.527
7.535
7.540
7.546
7.548
7.566
7.583
7.586
7.730
7.733
7.748
7.751
7.754
7.768
7.772
7.975
7.995
8.484
8.486
8.504
8.506
2.09
3.09
2.07
4.65
1.99
2.01
4.01
1.04
0.99
0.98
7.07.27.47.67.88.08.28.48.68.8 ppm
7.26
27.
313
7.31
77.
322
7.32
57.
331
7.33
77.
500
7.50
97.
512
7.51
87.
527
7.53
57.
540
7.54
67.
548
7.56
67.
583
7.58
67.
730
7.73
37.
748
7.75
17.
754
7.76
87.
772
7.97
57.
995
8.48
48.
486
8.50
48.
506
2.00
8
4.01
4
1.03
5
0.98
7
0.97
6
!
N
O
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S53
13C NMR spectrum of 3ai (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
25.81
26.11
30.66
37.48
52.57
76.69
77.00
77.21
77.32
102.56
125.63
126.41
127.54
128.29
128.47
129.14
129.85
132.97
135.42
136.04
142.38
162.15
!
N
O
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S54
1H NMR spectrum of 3aj (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
0.355
0.366
0.370
0.382
0.941
0.946
0.952
0.959
0.961
0.967
0.978
0.987
0.991
0.996
1.008
1.016
3.816
3.833
7.262
7.351
7.355
7.363
7.368
7.374
7.504
7.511
7.515
7.522
7.529
7.536
7.542
7.554
7.572
7.717
7.721
7.738
7.756
7.759
7.964
7.973
7.984
8.487
8.489
8.507
8.509
2.04
2.07
1.09
2.08
2.14
4.22
1.06
1.03
1.00
7.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.8 ppm
7.26
27.
351
7.35
57.
363
7.36
87.
374
7.50
47.
511
7.51
57.
522
7.52
97.
536
7.54
27.
554
7.57
27.
717
7.72
17.
738
7.75
67.
759
7.96
47.
973
7.98
4
8.48
78.
489
8.50
78.
509
2.13
8
4.21
9
1.06
2
1.02
7
1.00
0
!
N
O
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S55
13C NMR spectrum of 3aj (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
4.16
10.68
50.80
76.68
77.00
77.32
102.35
125.71
126.35
127.48
128.23
128.60
129.24
129.67
132.98
135.44
136.17
142.03
162.07
!
N
O
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S56
1H NMR spectrum of 3ak (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
3.183
3.519
3.535
3.550
4.041
4.057
4.073
7.263
7.335
7.339
7.345
7.347
7.352
7.359
7.503
7.508
7.516
7.519
7.526
7.530
7.534
7.543
7.547
7.554
7.557
7.572
7.574
7.592
7.595
7.745
7.748
7.763
7.765
7.768
7.783
7.786
7.982
8.002
8.482
3.05
2.08
2.07
2.03
2.96
1.17
1.07
1.02
1.00
7.27.47.67.88.08.28.48.6 ppm
7.26
37.
335
7.33
97.
345
7.34
77.
352
7.35
97.
503
7.50
87.
516
7.51
97.
526
7.53
07.
534
7.54
37.
547
7.55
47.
557
7.57
27.
574
7.59
27.
595
7.74
57.
748
7.76
37.
765
7.76
87.
783
7.78
67.
982
8.00
2
8.48
28.
484
8.50
28.
504
2.03
2
2.95
71.
166
1.07
0
1.01
7
1.00
0
!
N
O
PhBr
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S57
13C NMR spectrum of 3ak (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
46.39
58.71
69.36
76.68
77.00
77.32
102.60
125.49
126.50
127.63
128.14
128.68
129.32
129.73
133.19
135.56
136.05
142.40
161.89
!
N
O
PhBr
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S58
1H NMR spectrum of 3al (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
3.318
7.262
7.316
7.319
7.330
7.335
7.339
7.510
7.512
7.519
7.523
7.527
7.531
7.548
7.561
7.568
7.570
7.586
7.588
7.732
7.735
7.752
7.755
7.770
7.773
7.973
7.994
8.489
8.491
8.509
3.14
2.06
4.22
1.06
1.03
1.00
7.47.67.88.08.28.48.6 ppm
7.26
27.
316
7.31
97.
330
7.33
57.
339
7.51
07.
512
7.51
97.
523
7.52
77.
531
7.54
87.
561
7.56
87.
570
7.58
67.
588
7.73
27.
735
7.75
27.
755
7.77
07.
773
7.97
37.
994
8.48
98.
491
8.50
98.
511
2.06
0
4.22
0
1.05
8
1.02
6
1.00
0
!
N
OMe
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S59
13C NMR spectrum of 3al (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
35.11
76.68
77.00
77.32
101.94
125.34
126.41
127.61
128.13
128.98
129.03
129.30
133.02
135.43
136.36
142.17
162.17
!
N
OMe
PhBr
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S60
1H NMR spectrum of 3ba (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm3.851
5.178
6.853
6.859
6.863
6.867
6.877
6.885
6.975
6.996
7.165
7.172
7.176
7.181
7.260
7.570
7.573
7.590
7.608
7.611
7.761
7.764
7.779
7.781
7.784
7.799
7.802
8.005
8.025
8.535
8.537
8.555
8.557
3.07
2.00
4.01
2.03
3.00
1.05
1.05
1.01
1.00
6.87.07.27.47.67.88.08.28.48.68.8 ppm
6.85
36.
859
6.86
36.
867
6.87
76.
885
6.97
56.
996
7.16
57.
172
7.17
67.
181
7.26
0
7.57
07.
573
7.59
07.
608
7.61
17.
761
7.76
47.
779
7.78
17.
784
7.79
97.
802
8.00
58.
025
8.53
58.
537
8.55
58.
557
4.01
3
2.03
3
2.99
8
1.05
1
1.04
7
1.01
1
1.00
0
!
N
O
Ph
BrOMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S61
13C NMR spectrum of 3ba (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
49.96
55.28
76.68
77.00
77.32
103.46
113.75
125.55
126.57
126.73
127.03
127.67
128.08
128.24
128.55
130.79
133.26
135.62
137.26
142.16
159.99
162.25
!
N
O
Ph
BrOMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S62
1H NMR spectrum of 3ca (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
2.404
5.155
6.848
6.854
6.862
6.871
6.955
6.975
7.147
7.157
7.164
7.173
7.176
7.248
7.557
7.560
7.577
7.595
7.598
7.747
7.750
7.768
7.771
7.785
7.789
7.995
8.015
8.529
8.531
8.549
8.551
3.11
2.00
2.03
2.05
5.15
1.06
1.05
1.02
1.00
6.87.07.27.47.67.88.08.28.48.68.8 ppm
6.84
86.
854
6.86
26.
871
6.95
56.
975
7.14
77.
157
7.16
47.
173
7.17
67.
248
7.55
77.
560
7.57
77.
595
7.59
87.
747
7.75
07.
768
7.77
17.
785
7.78
97.
995
8.01
5
8.52
98.
531
8.54
98.
551
2.03
1
2.05
2
5.14
6
1.06
4
1.04
8
1.02
2
1.00
0
!
N
O
Ph
BrMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S63
13C NMR spectrum of 3ca (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
21.42
49.98
76.68
77.00
77.32
102.93
125.54
126.53
126.72
127.00
127.65
128.22
128.54
129.10
129.27
132.81
133.25
135.63
137.22
139.20
142.41
162.18
!
N
O
Ph
BrMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S64
1H NMR spectrum of 3da (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
5.166
6.814
6.823
6.832
6.837
7.024
7.034
7.044
7.067
7.169
7.178
7.185
7.194
7.259
7.593
7.596
7.614
7.631
7.634
7.774
7.778
7.795
7.798
7.813
7.816
8.000
8.020
8.551
8.553
8.571
8.574
2.00
2.05
4.06
3.03
1.04
1.05
1.03
1.00
6.66.87.07.27.47.67.88.08.28.48.68.8 ppm
6.81
46.
823
6.83
26.
837
7.02
47.
034
7.04
47.
067
7.16
97.
178
7.18
57.
194
7.25
9
7.59
37.
596
7.61
47.
631
7.63
47.
774
7.77
87.
795
7.79
87.
813
7.81
6
8.00
08.
020
8.55
18.
553
8.57
18.
574
2.04
6
4.05
8
3.02
6
1.03
9
1.05
4
1.03
2
1.00
0
!
N
O
Ph
BrF
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S65
13C NMR spectrum of 3da (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
49.85
76.68
77.00
77.32
103.33
115.45
115.67
125.58
126.59
126.62
127.18
127.93
128.34
128.61
131.48
131.56
131.60
131.63
133.37
135.42
136.98
141.15
161.64
162.14
164.13
!
N
O
Ph
BrF
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S66
1H NMR spectrum of 3ea (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
1.403
1.421
1.439
4.389
4.407
4.425
4.442
5.147
6.797
6.806
6.815
6.820
7.140
7.162
7.166
7.175
7.180
7.261
7.600
7.602
7.620
7.638
7.640
7.779
7.782
7.800
7.818
7.821
7.997
8.017
8.029
8.050
8.554
8.556
8.574
8.576
3.11
2.18
1.97
2.03
5.05
1.14
1.15
3.11
1.00
6.87.07.27.47.67.88.08.28.48.6 ppm
6.79
76.
806
6.81
56.
820
7.14
07.
162
7.16
67.
175
7.18
07.
261
7.60
07.
602
7.62
07.
638
7.64
07.
779
7.78
27.
800
7.81
87.
821
7.99
78.
017
8.02
98.
050
8.55
48.
556
8.57
48.
576
2.02
6
5.04
8
1.13
9
1.14
8
3.10
9
1.00
0
!
N
O
Ph
BrCO2Et
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S67
13C NMR spectrum of 3ea (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
14.28
49.88
61.31
76.68
77.00
77.32
102.63
125.60
126.59
127.24
128.06
128.40
128.65
129.60
129.70
131.15
133.44
135.39
136.78
139.71
141.18
162.06
165.84
!
N
O
Ph
BrCO2Et
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S68
1H NMR spectrum of 3fa (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
5.142
6.767
6.773
6.787
7.144
7.148
7.157
7.171
7.175
7.184
7.255
7.595
7.609
7.615
7.626
7.644
7.646
7.781
7.785
7.802
7.820
7.823
7.995
8.015
8.557
8.559
8.578
8.579
2.06
2.01
4.86
3.14
1.24
1.03
1.00
6.57.07.58.08.59.0 ppm
6.76
76.
773
6.78
77.
144
7.14
87.
157
7.17
17.
175
7.18
47.
255
7.59
57.
609
7.61
57.
626
7.64
47.
646
7.78
17.
785
7.80
27.
820
7.82
37.
995
8.01
5
8.55
78.
559
8.57
88.
579
2.00
7
4.85
7
3.14
1
1.24
2
1.03
0
1.00
0
!
N
O
Ph
BrCF3
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S69
13C NMR spectrum of 3fa (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
49.86
76.68
77.00
77.32
102.85
119.63
122.34
125.05
125.32
125.36
125.40
125.43
125.65
126.56
126.63
127.31
127.79
128.19
128.44
128.69
130.15
130.82
131.14
131.47
131.80
133.50
135.32
136.77
138.97
140.64
162.06
!
N
O
Ph
BrCF3
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S70
1H NMR spectrum of 3ga (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
3.563
4.923
4.960
5.367
5.405
6.462
6.724
6.743
6.845
6.854
6.860
6.869
6.878
6.890
6.949
6.951
6.955
6.957
6.970
6.972
6.976
6.978
7.162
7.172
7.178
7.186
7.188
7.193
7.197
7.259
7.288
7.308
7.328
7.582
7.585
7.601
7.603
7.621
7.623
7.770
7.774
7.789
7.791
3.07
1.00
0.98
1.00
1.00
2.01
1.04
3.00
1.04
1.04
1.04
1.01
1.00
6.46.66.87.07.27.47.67.88.08.28.48.68.8 ppm
6.46
26.
724
6.74
36.
845
6.85
46.
860
6.86
96.
878
6.89
06.
949
6.95
16.
955
6.95
76.
970
6.97
26.
976
6.97
87.
162
7.17
27.
178
7.18
67.
188
7.19
37.
197
7.25
97.
288
7.30
87.
328
7.58
27.
585
7.60
17.
603
7.62
17.
623
7.77
07.
774
7.78
97.
791
7.79
47.
809
7.81
28.
011
8.03
1
8.54
88.
551
8.56
88.
571
0.99
5
1.00
1
2.01
0
1.03
6
3.00
5
1.03
6
1.03
8
1.03
5
1.01
0
1.00
0
!
N
O
Ph
Br
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S71
13C NMR spectrum of 3ga (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
50.02
55.02
76.68
77.00
77.32
102.55
114.33
115.70
121.51
125.51
126.54
126.67
127.00
127.75
128.26
128.55
129.58
133.30
135.55
136.59
137.42
142.04
159.23
162.16
!
N
O
Ph
Br
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S72
1H NMR spectrum of 3ha (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
3.545
4.915
4.953
5.310
5.348
6.829
6.838
6.840
6.847
6.853
6.889
6.898
6.910
6.921
6.931
7.124
7.129
7.134
7.141
7.150
7.259
7.404
7.414
7.417
7.425
7.427
7.435
7.437
7.448
7.562
7.565
7.583
7.600
7.603
7.744
7.748
7.762
7.765
7.768
7.783
3.08
1.01
1.02
2.07
3.06
3.08
1.09
1.06
1.04
1.03
1.00
6.66.87.07.27.47.67.88.08.28.48.68.8 ppm
6.82
96.
838
6.84
06.
847
6.85
36.
889
6.89
86.
910
6.92
16.
931
7.12
47.
129
7.13
47.
141
7.15
07.
259
7.40
47.
414
7.41
77.
425
7.42
77.
435
7.43
77.
448
7.56
27.
565
7.58
37.
600
7.60
37.
744
7.74
87.
762
7.76
57.
768
7.78
37.
786
7.99
08.
010
8.54
98.
551
8.56
98.
571
2.07
1
3.05
7
3.07
7
1.08
7
1.05
7
1.04
2
1.02
6
1.00
0
!
N
O
Br
Ph
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S73
13C NMR spectrum of 3ha (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
49.82
55.21
76.68
77.00
77.32
103.33
110.89
120.35
124.54
125.63
126.44
126.86
127.12
127.50
127.98
128.48
131.08
131.26
133.03
135.75
137.24
139.68
156.47
162.45
!
N
O
Br
Ph
OMe
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S74
1H NMR spectrum of 3ia (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
4.471
4.509
5.784
5.823
6.815
6.820
6.834
6.837
6.852
6.856
7.115
7.119
7.123
7.129
7.137
7.141
7.150
7.155
7.168
7.173
7.176
7.192
7.195
7.254
7.280
7.284
7.300
7.304
7.319
7.323
7.601
7.604
7.619
7.621
7.623
7.639
7.642
7.674
7.677
7.694
7.697
7.772
7.776
1.01
1.00
3.03
4.11
1.06
1.05
1.02
1.04
1.02
1.00
6.66.87.07.27.47.67.88.08.28.48.68.8 ppm
6.81
56.
820
6.83
46.
837
6.85
26.
856
7.11
57.
119
7.12
37.
129
7.13
77.
141
7.15
07.
155
7.16
87.
173
7.17
67.
192
7.19
57.
254
7.28
07.
284
7.30
07.
304
7.31
97.
323
7.60
17.
604
7.61
97.
621
7.62
37.
639
7.64
27.
674
7.67
77.
694
7.69
77.
772
7.77
67.
790
7.79
37.
796
7.81
17.
814
8.00
58.
024
8.02
5
8.57
48.
576
8.59
48.
596
3.03
0
4.11
3
1.06
5
1.04
5
1.02
2
1.03
7
1.01
7
1.00
0
!
N
O
Br
Ph
Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S75
13C NMR spectrum of 3ia (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
49.72
76.68
77.00
77.32
103.40
123.89
125.80
126.64
127.02
127.18
127.22
128.05
128.23
128.64
130.90
132.05
132.72
133.30
135.42
136.35
136.90
140.80
162.22
!
N
O
Br
Ph
Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S76
1H NMR spectrum of 3ja (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
5.005
5.043
5.310
5.348
6.760
6.777
7.083
7.087
7.104
7.123
7.138
7.149
7.155
7.165
7.169
7.186
7.189
7.253
7.493
7.514
7.531
7.534
7.544
7.547
7.564
7.567
7.581
7.584
7.597
7.599
7.617
7.635
7.637
7.670
7.690
7.706
7.780
7.783
7.800
7.818
1.00
1.00
1.98
4.08
2.12
1.05
1.16
1.16
1.07
2.18
1.06
1.00
6.66.87.07.27.47.67.88.08.28.48.68.89.0 ppm
6.76
06.
777
7.08
37.
087
7.10
47.
123
7.13
87.
149
7.15
57.
165
7.16
97.
186
7.18
97.
253
7.49
37.
514
7.53
17.
534
7.54
47.
547
7.56
47.
567
7.58
17.
584
7.59
77.
599
7.61
77.
635
7.63
77.
670
7.69
07.
706
7.78
07.
783
7.80
07.
818
7.82
17.
838
7.85
97.
878
7.89
88.
022
8.04
3
8.57
78.
595
8.59
7
1.98
1
4.08
3
2.11
91.
051
1.16
51.
161
1.07
42.
178
1.06
2
1.00
0
!
N
O
Ph
Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S77
13C NMR spectrum of 3ja (400 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
50.11
76.68
77.00
77.32
103.06
125.61
126.45
126.57
126.62
126.82
127.07
127.13
127.76
127.81
128.22
128.36
128.60
129.43
132.59
132.81
133.11
133.34
135.61
137.21
142.19
162.24
!
N
O
Ph
Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S78
1H NMR spectrum of 3ka (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
0.893
0.910
0.928
1.318
1.335
1.352
1.360
1.368
1.378
1.398
1.406
1.571
1.589
1.613
1.629
1.647
2.876
2.897
2.917
5.501
7.135
7.153
7.229
7.247
7.258
7.265
7.292
7.311
7.328
7.490
7.492
7.510
7.527
7.530
7.716
7.719
7.737
7.739
7.754
7.758
7.965
7.986
8.450
8.452
8.470
8.472
3.07
4.14
2.55
2.04
1.93
2.04
1.46
1.99
1.05
1.04
1.00
1.00
7.07.27.47.67.88.08.28.48.6 ppm
7.13
57.
153
7.22
97.
247
7.25
87.
265
7.29
27.
311
7.32
87.
490
7.49
27.
510
7.52
77.
530
7.71
67.
719
7.73
77.
739
7.75
47.
758
7.96
57.
986
8.45
08.
452
8.47
08.
472
2.03
9
1.46
01.
994
1.05
1
1.04
0
0.99
9
1.00
0
!
N
O
Ph
n-C5H11Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S79
13C NMR spectrum of 3ka (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
22.10
22.74
25.12
27.82
36.93
46.59
76.68
77.00
77.32
102.30
123.47
125.68
126.40
127.58
128.12
128.73
129.31
129.39
133.01
134.11
135.41
136.03
142.08
161.62
!
N
O
Ph
n-C5H11Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S80
1H NMR spectrum of 3la (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
0.000
1.010
1.179
1.187
1.195
1.211
1.219
1.228
1.252
1.408
1.577
1.610
1.687
1.713
1.778
1.845
2.039
2.485
2.507
2.516
2.539
2.548
2.570
2.579
3.025
3.047
3.056
3.064
5.566
6.998
7.017
7.183
7.201
7.229
7.247
7.251
7.265
7.302
7.321
7.339
7.491
7.494
7.511
7.529
7.531
7.697
7.701
7.716
7.718
7.721
7.736
7.739
8.047
8.067
8.464
8.466
8.484
8.486
1.92
1.70
2.06
1.24
2.80
1.02
2.05
1.03
0.27
2.09
0.45
2.27
1.62
2.05
0.25
1.05
1.27
1.24
0.22
1.00
7.07.27.47.67.88.08.28.48.68.8 ppm
6.99
87.
017
7.18
37.
201
7.22
97.
247
7.25
17.
265
7.28
27.
302
7.32
17.
339
7.43
57.
454
7.47
37.
491
7.49
47.
511
7.52
97.
531
7.69
77.
701
7.71
67.
718
7.72
17.
736
7.73
9
8.04
78.
067
8.33
38.
353
8.46
48.
466
8.48
48.
486
0.45
3
2.26
8
1.62
2
2.05
3
0.25
1
1.04
6
1.26
5
1.24
4
0.22
2
1.00
0
!
N
O
Ph
Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S81
13C NMR spectrum of 3la (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
25.39
26.75
27.91
43.08
48.62
76.68
77.00
77.32
101.92
124.57
125.82
126.16
127.16
127.26
128.36
128.75
133.04
136.22
137.56
145.18
162.98
!
N
O
Ph
Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S82
1H NMR spectrum of 3ma (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
0.963
0.975
0.978
0.990
1.237
1.248
1.252
1.269
1.273
1.286
1.590
1.609
1.624
1.630
1.639
1.645
1.651
1.660
1.666
1.681
5.806
7.129
7.147
7.201
7.212
7.219
7.225
7.237
7.260
7.276
7.279
7.293
7.297
7.300
7.502
7.504
7.522
7.540
7.542
7.712
7.716
7.731
7.733
7.736
7.751
7.754
8.012
8.033
8.445
8.447
8.465
1.96
1.98
1.06
2.02
2.01
3.93
1.06
1.06
1.00
1.00
7.07.27.47.67.88.08.28.48.68.8 ppm
7.12
97.
147
7.20
17.
212
7.21
97.
225
7.23
77.
260
7.27
67.
279
7.29
37.
297
7.30
07.
502
7.50
47.
522
7.54
07.
542
7.71
27.
716
7.73
17.
733
7.73
67.
751
7.75
4
8.01
28.
033
8.44
58.
447
8.46
58.
467
2.00
7
3.93
2
1.06
1
1.06
1
0.99
8
1.00
0
!
N
O
Ph
Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S83
13C NMR spectrum of 3ma (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
12.07
15.25
47.49
76.68
77.00
77.32
105.53
125.06
126.04
126.25
127.03
127.32
128.33
128.61
133.01
135.77
137.60
141.29
162.49
!
N
O
Ph
Br
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S84
1H NMR spectrum of 3na (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
2.957
5.111
6.800
6.808
6.818
7.035
7.053
7.148
7.157
7.162
7.256
7.334
7.352
7.370
7.394
7.411
7.433
7.452
7.472
7.557
7.575
8.531
8.551
3.21
2.01
2.07
2.05
3.11
2.12
1.03
1.22
1.08
1.00
6.66.87.07.27.47.67.88.08.28.48.6 ppm
6.80
06.
808
6.81
8
7.03
57.
053
7.14
87.
157
7.16
27.
256
7.33
47.
352
7.37
07.
394
7.41
17.
433
7.45
27.
472
7.55
77.
575
8.53
18.
551
2.06
9
2.04
8
3.10
7
2.12
31.
032
1.22
0
1.08
3
1.00
0
!
N
O
Ph
Me BrPh
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S85
13C NMR spectrum of 3na (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
25.62
50.20
76.69
77.00
77.32
100.11
126.78
127.02
127.30
127.33
127.56
128.19
128.48
128.94
129.51
134.23
135.32
136.75
137.11
137.54
142.69
162.29
!
N
O
Ph
Me BrPh
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S86
1H NMR spectrum of 3oa (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
5.134
6.144
6.805
6.814
6.823
6.829
7.043
7.060
7.154
7.160
7.163
7.170
7.180
7.261
7.330
7.347
7.367
7.399
7.402
7.405
7.422
7.436
7.439
7.900
2.06
2.11
2.14
2.05
3.16
1.43
2.24
2.17
1.00
5.56.06.57.07.58.0 ppm
5.13
4
6.14
4
6.80
56.
814
6.82
36.
829
7.04
37.
060
7.15
47.
160
7.16
37.
170
7.18
07.
261
7.33
07.
347
7.36
77.
399
7.40
27.
405
7.42
27.
436
7.43
9
7.90
0
2.05
8
2.10
6
2.14
4
2.04
7
3.15
6
1.43
22.
238
2.17
2
1.00
0
!
N
O
Ph
PhBr
O
O
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S87
13C NMR spectrum of 3oa (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
50.04
76.68
77.00
77.32
102.11
102.44
105.11
106.33
121.21
126.70
127.02
128.22
128.38
129.14
129.54
133.19
135.76
137.22
141.03
148.36
152.80
161.29
!
N
O
Ph
PhBr
O
O
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S88
1H NMR spectrum of 3pa (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm3.970
5.160
6.822
6.831
6.840
6.845
7.063
7.081
7.154
7.163
7.170
7.253
7.330
7.348
7.352
7.359
7.367
7.375
7.382
7.400
7.418
7.924
7.947
7.961
7.967
2.93
1.96
1.98
2.00
3.17
3.21
1.09
1.97
6.66.87.07.27.47.67.88.08.2 ppm
6.82
26.
831
6.84
06.
845
7.06
37.
081
7.15
47.
163
7.17
07.
253
7.33
07.
348
7.35
27.
359
7.36
77.
375
7.38
27.
400
7.41
8
7.92
47.
947
7.96
17.
967
1.98
1
2.00
0
3.16
9
3.20
7
1.08
6
1.96
6
!
N
O
Ph
PhBr
MeO
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S89
13C NMR spectrum of 3pa (100 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
50.14
55.79
76.68
77.00
77.32
102.74
108.37
123.56
126.74
127.04
128.24
128.37
128.40
129.12
129.62
129.76
135.67
137.20
139.72
159.43
161.87
!
N
O
Ph
PhBr
MeO
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S90
1H NMR spectrum of 3qa (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm5.149
6.808
6.819
6.827
6.832
7.056
7.073
7.153
7.162
7.166
7.174
7.180
7.189
7.262
7.348
7.366
7.386
7.420
7.423
7.426
7.441
7.457
7.460
7.482
7.489
7.502
7.504
7.509
7.511
7.524
7.531
8.018
8.031
8.041
8.053
2.04
2.01
1.96
3.00
2.05
1.06
1.06
1.03
1.00
6.66.87.07.27.47.67.88.08.28.4 ppm
6.80
86.
819
6.82
76.
832
7.05
67.
073
7.15
37.
162
7.16
67.
174
7.18
07.
189
7.26
27.
348
7.36
67.
386
7.42
07.
423
7.42
67.
441
7.45
77.
460
7.48
27.
489
7.50
27.
504
7.50
97.
511
7.52
47.
531
8.01
88.
031
8.04
18.
053
8.19
78.
204
8.22
08.
227
2.00
5
1.95
9
3.00
4
2.04
7
1.05
6
1.05
9
1.03
3
1.00
0
!
N
O
Ph
PhBr
F
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S91
13C NMR spectrum of 3qa (400 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
50.16
76.68
77.00
77.32
102.09
113.58
113.82
121.72
121.95
126.76
127.05
127.13
127.18
128.29
128.47
129.32
129.40
129.52
132.22
135.39
136.89
141.50
141.52
160.77
161.38
161.42
163.25
!
N
O
Ph
PhBr
F
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S92
1H NMR spectrum of 3ra (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
5.282
6.803
6.809
6.815
6.823
6.827
7.036
7.054
7.131
7.135
7.140
7.144
7.153
7.162
7.168
7.171
7.179
7.184
7.260
7.367
7.386
7.405
7.419
7.422
7.440
7.444
7.448
7.451
7.458
7.460
7.466
7.482
7.485
7.488
7.596
7.599
7.614
7.617
7.620
1.99
2.01
1.96
3.02
2.23
1.85
1.04
0.99
1.00
6.46.66.87.07.27.47.67.88.08.28.48.68.8 ppm
6.80
36.
809
6.81
56.
823
6.82
77.
036
7.05
47.
131
7.13
57.
140
7.14
47.
153
7.16
27.
168
7.17
17.
179
7.18
47.
260
7.36
77.
386
7.40
57.
419
7.42
27.
440
7.44
47.
448
7.45
17.
458
7.46
07.
466
7.48
27.
485
7.48
87.
596
7.59
97.
614
7.61
77.
620
7.63
57.
638
7.73
77.
759
8.43
58.
436
8.45
58.
456
2.01
2
1.96
1
3.01
7
2.23
1
1.84
6
1.03
9
0.99
5
1.00
0
!
NO
O
PhBr
Ph
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S93
13C NMR spectrum of 3ra (400 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
49.97
76.68
77.00
77.32
95.48
112.83
123.39
123.49
123.62
126.98
127.29
128.29
128.32
128.58
129.31
129.53
129.83
134.35
136.72
142.70
143.32
154.08
156.92
!
NO
O
PhBr
Ph
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S94
1H NMR spectrum of 3sa (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
5.172
6.821
6.831
6.840
6.845
7.085
7.088
7.106
7.165
7.175
7.179
7.187
7.192
7.263
7.371
7.374
7.391
7.410
7.439
7.442
7.445
7.461
7.476
7.479
7.482
7.523
7.535
7.543
7.555
8.801
8.805
8.821
8.825
2.08
1.99
2.00
3.10
2.26
1.27
1.21
1.01
1.00
6.66.87.07.27.47.67.88.08.28.48.68.89.09.2 ppm
6.82
16.
831
6.84
06.
845
7.08
57.
088
7.10
67.
165
7.17
57.
179
7.18
77.
192
7.26
37.
371
7.37
47.
391
7.41
07.
439
7.44
27.
445
7.46
17.
476
7.47
97.
482
7.52
37.
535
7.54
37.
555
8.80
18.
805
8.82
18.
825
9.08
49.
088
9.09
59.
100
1.99
3
1.99
6
3.09
7
2.25
8
1.26
51.
207
1.01
2
1.00
0
!
N
N
PhBr
O
Ph
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S95
13C NMR spectrum of 3sa (400 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
50.04
76.68
77.00
77.32
104.68
121.38
122.63
126.67
127.25
128.29
128.51
129.05
129.42
135.02
136.57
137.05
146.18
150.24
155.08
162.15
!
N
N
PhBr
O
Ph
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S96
1H NMR spectrum of 4sa (400 MHz, CDCl3)
10 9 8 7 6 5 4 3 2 1 ppm
5.244
6.724
6.884
6.889
6.898
6.907
7.166
7.175
7.181
7.189
7.192
7.197
7.201
7.218
7.221
7.239
7.263
7.342
7.344
7.362
7.381
7.409
7.413
7.416
7.420
7.429
7.434
7.440
7.450
7.453
8.726
8.729
8.730
8.746
1.95
1.00
1.93
2.92
1.97
2.08
2.04
0.96
1.01
6.66.87.07.27.47.67.88.08.28.48.68.89.09.2 ppm
6.72
46.
884
6.88
96.
898
6.90
77.
166
7.17
57.
181
7.18
97.
192
7.19
77.
201
7.21
87.
221
7.23
97.
263
7.34
27.
344
7.36
27.
381
7.40
97.
413
7.41
67.
420
7.42
97.
434
7.44
07.
450
7.45
3
8.72
68.
729
8.73
08.
746
8.74
98.
922
8.92
68.
933
8.93
8
1.00
0
1.92
9
2.91
91.
965
2.07
92.
044
0.95
9
1.00
7
!
N
N
PhH
O
Ph
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
4. 1H and 13C NMR spectrum of new compounds
S97
13C NMR spectrum of 4sa (400 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
48.65
76.68
77.00
77.32
109.81
120.85
121.65
126.75
127.09
128.33
128.84
129.20
135.19
136.56
137.08
147.78
152.88
154.84
163.15
!
N
N
PhH
O
Ph
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012