Supporting Information. Masahiro Egi, Kenji Azechi, Moriaki Saneto, Kaori Shimizu, and Shuji Akai*

Transcription

1 Supporting Information Cationic Gold(I)-Catalyzed Intramolecular Cyclization of -Hydroxyalkynones into 3(2H)-Furanones Masahiro Egi, Kenji Azechi, Moriaki Saneto, Kaori Shimizu, and Shuji Akai* School of Pharmaceutical Sciences, University of Shizuoka, 52-1, Yada, Suruga-ku, Shizuoka, Shizuoka , Japan Contents Experimental Section General procedure for the preparation of 3(2H)-furanones and 2,3-dihydro-4H-pyran- S2 4-ones Spectroscopic data for 3(2H)-furanones 2a i S2 S3 Spectroscopic data for 2,3-dihydro-4H-pyran-4-ones 4a,b S4 Preparation of γ-hydroxyalkynones 1a i S4 S6 Preparation of δ-hydroxyalkynones 3a,b S7 1 H and 13 C NMR chart for 3(2H)-furanones 2a i S8 S25 1 H and 13 C NMR chart for 2,3-dihydro-4H-pyran-4-ones 4a,b S26 S29 1 H and 13 C NMR chart for γ-hydroxyalkynones 1a i S30 S47 1 H and 13 C NMR chart for δ-hydroxyalkynones 3a,b S48 S51 S1

2 General procedure for the preparation of 3(2H)-furanones and 2,3-dihydro-4H-pyran-4-ones To a solution of γ-hydroxyalkynones 1 or δ-hydroxyalkynones 3 (0.50 mmol) in toluene (2.5 ml, 0.20 M) were added (p-cf 3 C 6 H 4 ) 3 PAuCl (17.5 mg, mmol) and AgOTf (6.4 mg, mmol) in this order at room temperature. The reaction mixture was stirred at room temperature until the complete consumption of 1 and then quenched with sat. aq. NH 4 Cl. The organic materials were extracted with EtOAc, and the combined organic extracts were washed with brine, dried over MgSO 4, and evaporated in vacuo. The residue was purified by column chromatography (silica gel, usually hexanes/etoac) to give 3(2H)-furanone 2 and 2,3-dihydro- 4H-pyran-4-ones 4. Spectroscopic data for 3(2H)-furanones 2-Methyl-5-phenylethyl-3(2H)-furanone (2a) A pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 1.43 (3H, d, J = 7.3 Hz), 2.82 (2H, t, J = 7.5 Hz), 2.98 (2H, t, J = 7.5 Hz), 4.48 (1H, q, J = 7.3 Hz), 5.39 (1H, s), (5H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 16.3, 32.0, 32.4, 82.5, 103.1, 126.6, 128.2, 128.6, 139.6, 192.3, 205.6; IR (CHCl 3 ) ν 3015, 2935, 1695, 1590 cm 1. HRMS (FAB) m/z calcd for C 13 H 14 O 2 [M] + : Found: ,2-Dimethyl-5-phenylethyl-3(2H)-furanone (2b) 1 A pale yellow solid, mp C; 1 H NMR (500 MHz, CDCl 3 ) δ 1.35 (6H, s), 2.81 (2H, t, J = 8.0 Hz), 2.97 (2H, t, J = 8.0 Hz), 5.32 (1H, s), (5H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 22.8, 32.1, 32.4, 88.6, 101.6, 126.6, 128.3, 128.6, 139.6, 190.4, 207.4; IR (CHCl 3 ) ν 3015, 2985, 2930, 1690, 1590 cm 1. 2,5-Dimethyl-2-phenyl-3(2H)-furanone (2c) 2 A pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 1.74 (3H, s), 2.33 (3H, s), 5.40 (1H, s), (3H, m), (2H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 16.9, 24.3, 90.4, 102.2, 124.5, 128.0, 128.5, 138.1, 188.5, 204.8; IR (CHCl 3 ) ν 3065, 3020, 1695, 1610 cm 1. 2,2-Dimethyl-5-(1,1-dimethylethyl)-3(2H)-furanone (2d) 3 A colorless solid, mp C; 1 H NMR (500 MHz, CDCl 3 ) δ 1.23 (9H, s), 1.35 (6H, s), 5.32 (1H, s); 13 C NMR (125 MHz, CDCl 3 ) δ 22.8, 27.4, 34.5, 88.4, 98.0, 199.0, 208.0; IR (CHCl 3 ) ν 3010, 2980, 1690, 1575 cm 1. 1 Reiter, M.; Turner, H.; Mills-Webb, R.; Gouverneur, V. J. Org. Chem. 2005, 70, Chimichi, S.; Boccalini, M.; Cosimelli, B.; Dall Acqua, F.; Viola, G. Tetrahedron 2003, 59, Sampson, P.; Roussis, V.; Drtina, G. J.; Koerwitz, F. L.; Wiemer, D. F. J. Org. Chem. 1986, 51, S2

3 2-Pentyl-1-oxaspiro[4,4]non-2-en-4-one (2e) 4 A yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 0.90 (3H, t, J = 7.2 Hz), (4H, m), (2H, m), (8H, m), 2.45 (2H, t, J = 7.4 Hz), 5.38 (1H, s); 13 C NMR (125 MHz, CDCl 3 ) δ 13.9, 22.2, 25.6, 25.7, 30.8, 31.2, 36.9, 98.5, 102.3, 192.3, 206.6; IR (CHCl 3 ) ν 2960, 2935, 1680, 1585 cm 1. HRMS (ESI) m/z calcd for C 13 H 20 O 2 Na [M+Na] + : Found: ,2-Dimethyl-5-phenyl-3(2H)-furanone (2f) 1 An off-white solid, mp C; 1 H NMR (500 MHz, CDCl 3 ) δ 1.49 (6H, s), 5.97 (1H, s), (3H, m), 7.84 (2H, d, J = 8.0 Hz); 13 C NMR (125 MHz, CDCl 3 ) δ 23.1, 89.0, 98.6, 127.2, 128.8, 129.2, 132.6, 183.4, 207.0; IR (CHCl 3 ) ν 3015, 2985, 1685, 1605 cm 1. 5-(4-Methoxyphenyl)-2,2-dimethyl-3(2H)-furanone (2g) 1 A pale yellow solid, mp C; 1 H NMR (500 MHz, CDCl 3 ) δ 1.48 (6H, s), 3.88 (3H, s), 5.85 (1H, s), 6.98 (2H, d, J = 8.8 Hz), 7.78 (2H, d, J = 8.8 Hz); 13 C NMR (125 MHz, CDCl 3 ) δ 23.2, 55.5, 88.8, 97.0, 114.2, 121.7, 129.1, 163.2, 183.3, 206.7; IR (CHCl 3 ) ν 3020, 2985, 1680, 1610 cm 1. (E)-2,2-Dimethyl-5-(2-phenylethenyl)-3(2H)-furanone (2h) 5 An orange solid, mp C; 1 H NMR (500 MHz, CDCl 3 ) δ 1.46 (6H, s), 5.59 (1H, s), 6.86 (1H, d, J = 16.0 Hz), (3H, m), 7.50 (1H, d, J = 16.0 Hz), (2H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 23.2, 88.5, 102.0, 116.4, 127.9, 129.0, 130.2, 134.7, 138.8, 181.3, 206.9; IR (CHCl 3 ) ν 3015, 2985, 1680, 1630 cm 1. 5-Phenylethyl-3(2H)-furanone (2i) A pale yellow oil; H NMR (500 MHz, CDCl 3 ) δ 2.84 (2H, t, J = 8.0 Hz), 2.98 (2H, t, J = 8.0 Hz), 4.50 (2H, s), 5.47 (1H, s), (5H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 31.9, 32.4, 75.2, 104.5, 126.6, 128.2, 128.7, 139.6, 194.0, 202.9; IR (CHCl 3 ) ν 3015, 2965, 1695, 1595 cm 1. HRMS (ESI) m/z calcd for C 12 H 12 O 2 Na [M+Na] + : Found: Binder, J. T.; Crone, B.; Kirsch, S. F.; Liébert, C.; Menz, H. Eur. J. Org. Chem. 2007, Inoue, Y.; Ohuchi, K.; Yen, I.-F.; Imaizumi, S. Bull. Chem. Soc. Jpn. 1989, 62, S3

4 Spectroscopic data for 2,3-dihydro-4H-pyran-4-ones 6-Phenyl-2,3-dihydro-4H-pyran-4-one (4a) A pale yellow solid, mp C; 1 H NMR (500 MHz, CDCl 3 ) δ 2.67 (2H, t, J = 7.0 Hz), 4.67 (2H, t, J = 7.0 Hz), 6.03 (1H, s), (3H, m), 7.74 (2H, d, J = 7.5 Hz); 13 C NMR (125 MHz, CDCl 3 ) δ 36.0, 68.2, 102.4, 126.5, 128.7, 131.7, 132.6, 170.5, 192.7; IR (CHCl 3 ) ν 3020, 1660, 1600 cm 1. HRMS (ESI) m/z calcd for C 11 H 10 O 2 Na [M+Na] + : Found: Phenylethyl-2,3-dihydro-4H-pyran-4-one (4b) A pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 2.51 (2H, t, J = 6.9 Hz), 2.55 (2H, t, J = 7.7 Hz), 2.88 (2H, t, J = 7.7 Hz), 4.45 (2H, t, J = 6.8 Hz), 5.30 (1H, s), (5H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 32.5, 35.7, 36.5, 68.0, 105.0, 126.4, 128.2, 128.5, 140.1, 176.5, 192.1; IR (CHCl 3 ) ν 3015, , 1605 cm 1. HRMS (ESI) m/z calcd for C 13 H 14 O 2 Na [M+Na] + : Found: General procedure for the preparation of γ-hydroxyalkynones To a solution of propargyl alcohols (9.0 mmol) in THF (15 ml) were added HMPA (36 mmol) and n-butyllithium (1.6 M in hexanes, 18 mmol) sequentially at 78 C under nitrogen atmosphere. After stirring for 30 min at 78 C, a solution of Weinreb amides (7.5 mmol) in THF (5.0 ml) was added. The reaction mixture was allowed to warm to room temperature, stirred until the complete consumption of Weinreb amides, and quenched with sat. aq. NH 4 Cl. The organic materials were extracted with EtOAc, and the combined organic extracts were washed with H 2 O several times and then brine, dried over MgSO 4, and evaporated in vacuo. The residue was purified by column chromatography (silica gel, usually hexanes/etoac) to give 1. Spectroscopic data for γ-hydroxyalkynones 6-Hydroxy-1-phenyl-4-heptyn-3-one (1a) 36% yield: Prepared from N-methoxy-N-methyl-3-phenylpropionamide and 3-butyn-2-ol. A pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 1.51 (3H, d, J = 6.3 Hz), 1.95 (1H, d, J = 5.7 Hz), (4H, m), (1H, m), (5H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 23.4, 29.7, 46.7, 58.1, 82.7, 93.0, 126.3, 128.3, 128.5, 140.0, 186.6; IR (CHCl 3 ) ν 3600, 3445, 3015, 2215, 1675 cm 1. HRMS (ESI) m/z calcd for C 13 H 14 O 2 Na [M+Na] + : Found: S4

5 6-Hydroxy-6-methyl-1-phenyl-4-heptyn-3-one (1b) 72% yield: Prepared from N-methoxy-N-methyl-3-phenylpropionamide and 2-methyl-3-butyn-2-ol. A pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 1.55 (6H, s), 2.10 (1H, br s), (4H, m), (5H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 29.8, 30.6, 46.8, 65.1, 81.0, 95.8, 126.3, 128.3, 128.5, 140.1, 186.8; IR (CHCl 3 ) ν 3595, 3020, 2990, 2210, 1675 cm 1. HRMS (ESI) m/z calcd for C 14 H 16 O 2 Na [M+Na] + : Found: Hydroxy-2,2,6-trimethyl-4-heptyn-3-one (1d) 70% yield: Prepared from N-methoxy-N-methylpivalamide and 2-methyl- 3-butyn-2-ol. A colorless oil; 1 H NMR (500 MHz, CDCl 3 ) δ 1.20 (9H, s), 1.58 (6H, s); 13 C NMR (125 MHz, CDCl 3 ) δ 26.0, 30.7, 44.8, 65.2, 79.1, 97.0, 194.1; IR (CHCl 3 ) ν 3595, 2970, 2215, 1670 cm 1. HRMS (ESI) m/z calcd for C 10 H 16 O 2 Na [M+Na] + : Found: (1-Hydroxycyclopentyl)-1-octyn-3-one (1e) 41% yield: Prepared from N-methoxy-N-methylhexanamide and 1-ethynylcyclopentanol. A pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 0.89 (3H, t, J = 7.0 Hz), (4H, m), (2H, m), (5H, m), (4H, m), 2.55 (2H, t, J = 7.4 Hz); 13 C NMR (125 MHz, CDCl 3 ) δ 13.9, 22.4, 23.56, 23.62, 31.1, 42.2, 45.4, 74.2, 82.2, 94.7, 188.2; IR (CHCl 3 ) ν 3590, 2960, 2210, 1670 cm 1. HRMS (ESI) m/z calcd for C 13 H 20 O 2 Na [M+Na] + : Found: Hydroxy-4-methyl-1-phenyl-2-pentyn-1-one (1f) 6 100% yield: Prepared from N-methoxy-N-methylbenzamide and 2-methyl-3-butyn- 2-ol. A yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 1.67 (6H, s), 2.52 (1H, br s), 7.48 (2H, t, J = 7.7 Hz), 7.61 (1H, t, J = 7.7 Hz), 8.11 (2H, d, J = 7.7 Hz); 13 C NMR (125 MHz, CDCl 3 ) δ 30.7, 65.3, 79.9, 98.0, 128.6, 129.6, 134.2, 136.5, 177.9; IR (CHCl 3 ) ν 3595, 3015, 2215, 1645 cm 1. 6 Saimoto, H.; Yasui, M.; Ohrai, S.; Oikawa, H.; Yokoyama, K.; Shigemasa, Y. Bull. Chem. Soc. Jpn. 1999, 72, S5

6 4-Hydroxy-1-(4-methoxyphenyl)-4-methyl-2-pentyn-1-one (1g) 80% yield: Prepared from 4,N-dimethoxy-N-methylbenzamide and 2-methyl- 3-butyn-2-ol. An off-white solid, mp C; 1 H NMR (500 MHz, CDCl 3 ) δ 1.66 (6H, s), 2.30 (1H, br s), 3.89 (3H, s), 6.95 (2H, d, J = 8.8 Hz), 8.08 (2H, d, J = 8.8 Hz); 13 C NMR (125 MHz, CDCl 3 ) δ 30.8, 55.6, 65.3, 79.9, 97.0, 113.9, 129.9, 132.0, 164.6, 176.5; IR (CHCl 3 ) ν 3595, 2990, 2210, 1640 cm 1. HRMS (ESI) m/z calcd for C 13 H 14 O 3 Na [M+Na] + : Found: (1E)-6-Hydroxy-6-methyl-1-phenyl-1-hepten-4-yn-3-one (1h) 95% yield: Prepared from (2E)-N-methoxy-N-methyl-2-propenamide and 2-methyl- 3-butyn-2-ol. A pale yellow solid, mp C; 1 H NMR (500 MHz, CDCl 3 ) δ 1.65 (6H, s), 6.77 (1H, d, J = 16.5 Hz), (3H, m), (2H, m), 7.79 (1H, d, J = 16.5 Hz); 13 C NMR (125 MHz, CDCl 3 ) δ 30.8, 65.2, 79.6, 96.5, 128.1, 128.7, 129.1, 131.2, 133.9, 148.9, 178.2; IR (CHCl 3 ) ν 3595, 3435, 3015, 2990, 2220, 1630 cm 1. HRMS (ESI) m/z calcd for C 14 H 14 O 2 Na [M+Na] + : Found: Hydroxy-1-phenyl-4-hexyn-3-one (1i) 55% yield: Prepared from N-methoxy-N-methyl-3-phenylpropionamide and 1-(tert-butyldimethylsilyloxy)-2-propyne, followed by AcOH desilylation. A pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 1.94 (1H, t, J = 6.3 Hz), 2.91 (2H, dt, J = 1.7, 7.7 Hz), 2.99 (2H, t, J = 7.7 Hz), 4.42 (2H, d, J = 6.3 Hz), (5H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 29.7, 46.6, 50.7, 84.3, 90.2, 126.3, 128.3, 128.5, 140.0, 186.6; IR (CHCl 3 ) ν 3605, 3015, 2220, 1675 cm 1. HRMS (ESI) m/z calcd for C 12 H 12 O 2 Na [M+Na] + : Found: Pd-catalyzed coupling of thioester with alkyne to furnish 5-hydroxy-5-phenyl-3-hexyn-2-one (1c) To a solution of S-dodecyl ethanethioate (130 mg, 0.53 mmol) in DMF (0.88 ml) and Et 3 N (0.18 ml) were added PdCl 2 (dppf) CH 2 Cl 2 (21.7 mg, mmol), P(2-furyl) 3 (15.4 mg, mmol), CuI (172 mg, 0.90 mmol), and 2-phenyl-3-butyn-2-ol (155 mg, 1.1 mmol) at room temperature. After stirring for 1.5 h at 50 C, the mixture was cooled to room temperature, diluted with Et 2 O and H 2 O, and filtered through Celite. The filtrate was washed with H 2 O several times and then brine, dried over MgSO 4, and evaporated in vacuo. The residue was purified by column chromatography (silica gel, hexanes/etoac = 5:1) to give 1c (84 mg, 84%). A pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 1.82 (3H, s), 2.37 (3H, s), (3H, m), (2H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 32.4, 32.6, 69.8, 83.6, 93.8, 124.7, 128.2, 128.5, 143.7, 184.5; IR (CHCl 3 ) ν 3585, 3445, 3065, 2220, 1680 cm 1. HRMS (ESI) m/z calcd for C 12 H 12 O 2 Na [M+Na] + : Found: S6

7 Preparation of δ-hydroxyalkynones 3a,b 5-Hydroxy-1-phenyl-2-pentyn-1-one (3a) To a solution of 3-butyn-1-ol (0.38 ml, 5.0 mmol) in THF (15 ml) was added EtMgBr (1.0 M in THF; 11mL, 11 mmol) at 0 C under nitrogen atmosphere, and the reaction was refluxed for 1.5 h. After cooling to 78 C, a solution of benzaldehyde (523 mg, 5.0 mmol) in THF (1.5 ml) was added. The mixture was allowed to warm to room temperature, stirred overnight, quenched with sat. aq. NH 4 Cl. The organic materials were extracted with EtOAc, and the combined organic extracts were washed with brine, dried over MgSO 4, and evaporated in vacuo. The residue was purified by column chromatography (silica gel, hexanes/etoac = 1:2) to give 1-phenyl-2-pentyne-1,5-diol (776 mg, 88%). To a solution of the obtained compound (103 mg, 0.58 mmol) in CH 2 Cl 2 (12 ml) was added BaMnO 4 (1.54 g, 6.0 mmol) at room temperature under nitrogen atmosphere. The reaction was stirred for 3.5 h and filtered through Celite. The filtrate was evaporated in vacuo. The residue was purified by column chromatography (silica gel, hexanes/etoac = 1:1) to give 3a (83.1 mg, 82%). A pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 2.08 (1H, br s), 2.78 (2H, t, J = 6.3 Hz), 3.91 (2H, t, J = 6.3 Hz), (2H, m), (1H, m), 8.14 (2H, dd, J = 1.2, 8.5 Hz); 13 C NMR (125 MHz, CDCl 3 ) δ 23.5, 60.3, 80.7, 93.2, 128.6, 129.6, 134.1, 136.6, 178.1; IR (CHCl 3 ) ν 3615, 3020, 2235, 2205, 1695, 1640 cm 1. HRMS (ESI) m/z calcd for C 11 H 10 O 2 Na [M+Na] + : Found: Hydroxy-1-phenyl-4-heptyn-3-one (3b) To a solution of 3-butyn-1-ol (0.421 ml, 5.6 mmol) in THF (5 ml) was added EtMgBr (1.0 M in THF; 11 ml, 11 mmol) at 0 C under nitrogen atmosphere, and the reaction was refluxed for 1.5 h. After cooling to 0 C, HMPA (2.5 ml, 14 mmol) and a solution of 3-phenylpropionaldehyde (306 mg, 2.3 mmol) in THF (5.0 ml) were added. The mixture was allowed to warm to room temperature, stirred for 4.5 h, quenched with sat. aq. NH 4 Cl. The organic materials were extracted with EtOAc, and the combined organic extracts were washed with H 2 O several times and then brine, dried over MgSO 4, and evaporated in vacuo. The residue was purified by column chromatography (silica gel, hexanes/etoac = 1:1) to give 7-phenyl-3-heptyne-1,5-diol (323 mg, 69%). To a solution of the obtained compound (116 mg, 0.57 mmol) in CH 2 Cl 2 (11 ml) was added BaMnO 4 (1.46 g, 5.7 mmol) at room temperature under nitrogen atmosphere. The reaction was stirred overnight and filtered through Celite. The filtrate was evaporated in vacuo. The residue was purified by column chromatography (silica gel, hexanes/etoac = 1:1) to give 3b (94.1 mg, 82%). A pale yellow oil; 1 H NMR (500 MHz, CDCl 3 ) δ 1.90 (1H, br s), 2.63 (2H, t, J = 6.0 Hz), (4H, m), (2H, m), (5H, m); 13 C NMR (125 MHz, CDCl 3 ) δ 23.3, 29.8, 46.8, 60.1, 81.9, 91.2, 126.3, 128.3, 128.5, 140.2, 187.0; IR (CHCl 3 ) ν 3620, 3455, 3020, 2950, 2220, 1670 cm 1. HRMS (ESI) m/z calcd for C 13 H 14 O 2 Na [M+Na] + : Found: S7

8 F:\NMR Furanone\Ysaneto NON_E3_FT.als 2-Methyl-5-phenethyl-3(2H)-furanone DATIM Wed Apr 23 20:22: EXMOD SINGL OBNUC 1H OFR MHz OBSET 0.00 KHz OBFIN Hz OBATN 511 PW usec PW usec POINT SPO SCANS 8 FREQU Hz PD sec BF 0.12 Hz IRFIN Hz IRATN 511 EXREF 7.26 ppm TMSP S8

9 F:\Saneto\Yka _ carbon.als 2-Methyl-5-phenethyl-3(2H)-furanone DATIM :31:09 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 944 FREQU Hz PD sec EXREF ppm TMSP S9

10 F:\NMR Furanone\Yegi als 2,2-dimethyl-5-phenylethyl-3(2H)furanone DATIM :35:23 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S10

11 F:\NMR Furanone\Yegi C.als 2,2-dimethyl-5-phenylethyl-3(2H)furanone DATIM :22:55 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 1000 FREQU Hz PD sec EXREF ppm TMSP S11

12 F:\NMR Furanone\Yka als 2,5-dimethyl-2-phenyl-3(2H)furanone DATIM :28:42 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S12

13 F:\NMR Furanone\Yka carbon.als 2,5-dimethyl-2-phenyl-3(2H)furanone DATIM :47:49 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 344 FREQU Hz PD sec EXREF ppm TMSP S13

14 F:\NMR Furanone\Yka als 5-(tert-butyl)-2,2-dimethyl-3(2H)furanone DATIM :43:32 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S14

15 F:\NMR Furanone\Yka carbon.als 5-(tert-butyl)-2,2-dimethyl-3(2H)furanone DATIM :01:31 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 330 FREQU Hz PD sec EXREF ppm TMSP S15

16 F:\NMR Furanone\Yka als 2-pentyl-1-oxaspiro[4,4]non-2-en-4-one DATIM :24:42 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec BF 0.12 Hz EXREF 7.26 ppm TMSP S16

17 F:\NMR Furanone\Yka carbon.als 2-pentyl-1-oxaspiro[4,4]non-2-en-4-one DATIM :50:25 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 383 FREQU Hz PD sec BF 0.12 Hz EXREF ppm TMSP S17

18 F:\NMR Furanone\Yegi-furanone (Ph,Me,Me).als 2,2-dimethyl-5-phenyl-3(2H)-furanone DATIM :50:35 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S18

19 F:\NMR Furanone\Yegi-furanone (Ph,Me,Me)-13C.als 2,2-dimethyl-5-phenyl-3(2H)-furanone DATIM :21:14 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 641 FREQU Hz PD sec EXREF ppm TMSP S19

20 F:\NMR Furanone\Yegi-furanone (MeOPh,Me,Me).als 5-(4-methoxyphenyl)-2,2-dimethyl-3(2H)-furanone DATIM :40:21 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S20

21 F:\NMR Furanone\Yegi-furanone (MeOPh,Me,Me)-13C.als 5-(4-methoxyphenyl)-2,2-dimethyl-3(2H)-furanone DATIM :27:56 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 1000 FREQU Hz PD sec EXREF ppm TMSP S21

22 F:\NMR Furanone\Yka als 2,2-Dimethyl-5-(2-phenylethenyl)-3(2H)-furanone DATIM :42:05 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec BF 0.12 Hz EXREF 7.26 ppm TMSP S22

23 F:\NMR Furanone\Yka carbon.als 2,2-Dimethyl-5-(2-phenylethenyl)-3(2H)-furanone DATIM :56:17 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 257 FREQU Hz PD sec BF 0.12 Hz EXREF ppm TMSP S23

24 F:\NMR Furanone\Yks als 5-phenethyl-3(2H)-furanone DATIM :03:52 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S24

25 F:\NMR Furanone\Yks carbon.als 5-phenethyl-3(2H)furanone DATIM :44:41 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 1999 FREQU Hz PD sec EXREF ppm TMSP S25

26 F:\NMR Furanone\Yks als 6-phenyl-2,3-dihydro-4-pyranone DATIM :55:38 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S26

27 F:\NMR Furanone\Yks carbon.als 6-phenyl-2,3-dihydro-4-pyranone DATIM :56:43 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 1466 FREQU Hz PD sec EXREF ppm TMSP S27

28 F:\NMR Furanone\Yks als 6-phenethyl-2,3-dihydro-4-pyranone DATIM :32:24 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec BF 0.12 Hz EXREF 7.26 ppm TMSP S28

29 F:\NMR Furanone\Yks als 6-phenethyl-2,3-dihydro-4-pyranone DATIM :48:06 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 1138 FREQU Hz PD sec BF 0.12 Hz EXREF ppm TMSP S29

30 F:\NMR Furanone\Yks als 6-hydroxy-1-phenyl-4-heptyn-3-one DATIM :09:29 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S30

31 F:\NMR Furanone\Yks als 6-hydroxy-1-phenyl-4-heptyn-3-one DATIM :48:48 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 2500 FREQU Hz PD sec EXREF ppm TMSP S31

32 F:\NMR Furanone\Yegi als 6-hydroxy-6-methyl-1-phenyl-4-heptyn-3-one DATIM :12:08 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S32

33 F:\NMR Furanone\Yegi C.als 6-hydroxy-6-methyl-1-phenyl-4-heptyn-3-one DATIM :59:40 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 1000 FREQU Hz PD sec EXREF ppm TMSP S33

34 F:\NMR Furanone\Yka als 5-hydroxy-5-phenyl-3-hexyn-2-one DATIM :08:05 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S34

35 F:\NMR Furanone\Yka carbon.als 5-hydroxy-5-phenyl-3-hexyn-2-one DATIM :22:20 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 254 FREQU Hz PD sec EXREF ppm TMSP S35

36 F:\NMR Furanone\Yegi-tertBu,Me,Me.als 6-hydroxy-2,2,6-trimethyl-4-heptyn-3-one DATIM :54:40 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S36

37 F:\NMR Furanone\Yegi-tertBu,Me,Me-13C.als 6-hydroxy-2,2,6-trimethyl-4-heptyn-3-one DATIM :42:36 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 1000 FREQU Hz PD sec EXREF ppm TMSP S37

38 F:\NMR Furanone\Yka als 1-(1-hydroxycyclopentyl)-1-octyn-3-one DATIM :03:03 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec BF 0.12 Hz EXREF 7.26 ppm TMSP S38

39 F:\NMR Furanone\Yka carbon.als 1-(1-hydroxycyclopentyl)-1-octyn-3-one DATIM :29:11 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 469 FREQU Hz PD sec BF 0.12 Hz EXREF ppm TMSP S39

40 F:\NMR Furanone\Yka als 4-hydroxy-4-methyl-1-phenyl-2-pentyn-1-one DATIM :07:37 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S40

41 F:\NMR Furanone\Yka carbon.als 4-hydroxy-4-methyl-1-phenyl-2-pentyn-1-one DATIM :32:44 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 457 FREQU Hz PD sec EXREF ppm TMSP S41

42 F:\NMR Furanone\Yegi-MeOPh,Me,Me.als 4-hydroxy-1-(4-methoxyphenyl)-4-methyl-2-pentyn-1-one DATIM :56:19 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S42

43 F:\NMR Furanone\Yegi-MeOPh,Me,Me-13C.als 4-hydroxy-1-(4-methoxyphenyl)-4-methyl-2-pentyn-1-one DATIM :35:44 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 820 FREQU Hz PD sec EXREF ppm TMSP S43

44 F:\NMR Furanone\Yka als 1-styryl-4-hydroxy-4-methyl-2-pentyn-1-one DATIM :19:36 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec BF 0.12 Hz EXREF 7.26 ppm TMSP S44

45 F:\NMR Furanone\Yka carbon.als 1-styryl-4-hydroxy-4-methyl-2-pentyn-1-one DATIM :32:58 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 237 FREQU Hz PD sec BF 0.12 Hz EXREF ppm TMSP S45

46 F:\NMR Furanone\Yks als 6-hydroxy-1-phenyl-4-hexyn-3-one DATIM :02:07 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S46

47 F:\NMR Furanone\Yka carbon.als 6-hydroxy-1-phenyl-4-hexyn-3-one DATIM :51:51 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 232 FREQU Hz PD sec EXREF ppm TMSP S47

48 F:\NMR Furanone\Yks als 5-hydroxy-1-phenyl-2-pentyn-1-one DATIM :37:48 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S48

49 F:\NMR Furanone\Yks als 1-phenyl-5-hydroxy-2-pentyn-1-one DATIM :51:09 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 1009 FREQU Hz PD sec BF 0.12 Hz EXREF ppm TMSP S49

50 F:\NMR Furanone\Yks pure3.als 7-hydroxy-1-phenyl-4-heptyn-3-one DATIM :37:52 EXMOD single_pulse.ex2 OBNUC 1H OFR MHz OBSET 2.41 KHz OBFIN 6.01 Hz PW usec POINT SPO SCANS 8 FREQU Hz PD sec EXREF 7.26 ppm TMSP S50

51 F:\NMR Furanone\Yks carbon.als 7-hydroxy-1-phenyl-4-heptyn-3-one DATIM :45:02 EXMOD single_pulse_dec OBNUC 13C OFR MHz OBSET 7.87 KHz OBFIN 4.21 Hz PW usec POINT SPO SCANS 1991 FREQU Hz PD sec EXREF ppm TMSP S51