Supporting Information

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1 Supporting Information Pd(OAc) 2 -catalyzed Lactonization of Arylacetamides Involving Oxidation of C H Bonds Takeshi Uemura, Takuya Igarashi, Moe Noguchi, Kaname Shibata, and Naoto Chatani* Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka (Received January 17, 2015; CL ; chatani@chem.eng.osaka-u.ac.jp) Copyright The Chemical Society of Japan

2 Supporting Information Contents I. General Information II. Materials III. Synthesis of Starting Materials IV. Typical Procedure V. Spectroscopic Data I. General Information. 1 H NMR and 13 C NMR spectra were recorded on a JEOL ECS-400 spectrometer in CDCl 3 with tetrachloroethane as the internal standard. Data are reported as follows: chemical shift in ppm ( ), multiplicity (s = singlet, d = doublet, t = triplet, and m = multiplet), coupling constant (Hz), and integration. Infrared spectra (IR) were obtained using a JASCO FT/IR-4200 spectrometer; absorptions are reported in reciprocal centimeters with the following relative intensities: s (strong), m (medium), or w (weak). Mass spectra and high resolution mass spectra (HRMS) were obtained on a JEOL JMS-700 spectrometer. Analytical gas chromatography (GC) was carried out on a Shimazu GC-2014 gas chromatograph, equipped with a flame ionization detector. Melting points were determined using a Yamato melting point apparatus. Column chromatography was performed with SiO 2 (silicycle SilicaFlash F60 ( mesh)). Some compounds were purified by LC-908HPLC (GPC). II. Materials. Toluene (Kanto Chemical) was purified by passage through activated alumina using a GlassContour Solvent Dispensing System. Pd(OAc) 2 (CAS ) was purchased from Wako Pure Chemicals. NaHCO 3 (CAS ), PhI(OAc) 2 (CAS ) were purchased from Nacalai Tesque. 8-methylquinoline (CAS ) was purchased from Tokyo Chemical Industry Co., Ltd. PhI(OAc) 2 was recrystallized according to literature procedures 1. III. Synthesis of Starring Materials. All amides containing an 8-aminomethylquinoline moiety were prepared by reacting the corresponding amide with 8-bromomethylquinoline. 1 a) Fa-Jie, Chen.; Sheng, Zhao.; Fang, Hu.; Kai, Chen.; Qi, Zhang.; Shuo-Qing Zhang.; Bing,-Feng, Shi. Chem. Sci. 2013, 4, b) Md. Hossain, D.; Kitamura, T. Synthesis 2005, 12, S1

3 General Procedure for the Preparation of Starting Amides. (1) The Procedure for the Preparation of 8-bromemethylquinoline. 2 To an over-dried 300 ml three-necked flask, 8-methyl quinolone (10.0 g, 69.8 mmol), benzoyl peroxide (0.843 g, 3.49 mmol) and cyclohexane (150 ml) were added under a N 2 atmosphere. N-bromosucimide (13.6 g, 76.8 mmol) was then added portion wise with stirring. The solution was refluxed for 10 h. Upon completion of the reaction, the reaction mixture was filtered, the filtrate washed with saturated aqueous NaHCO 3 (3x100 ml) and brine (100 ml), and dried over anhydrous Na 2 SO 4. The solvent was evaporated in vacuio. Recrystallization from Et 2 O and hexane afforded a light brownish solid (7.1 g, 46%). (2) General Procedure for the Preparation of Starting Amide. 3 To an over-dried 100 ml three-necked flask, the carboxylic acid (10 mmol), DMF (5 drops) and DCM (30 ml) were added under a N 2 atmosphere. Oxalyl chloride (1.0 ml, 12 mmol) was added dropwise at 0 o C resulting in vigorous bubbling. The mixture was stirred for 3 h at room temperature, and the solvent was then removed in vacuo. The resulting acid chloride was used immediately without further purification. To a solution of the acid chloride in DCM (30 ml),a solution of 1,1,1,3,3,3-hexamethyldisilazane (30 mmol) in DCM (10 ml) was added dropwise at 0 o C, and the solution was then allowed to warm to room temperature. After stirring overnight, the reaction system was quenched with 1 M HCl aq. and saturated aqueous NH 4 Cl (excess amount) and the organic layer was separated. The aqueous layer was extracted with DCM (2x15 ml). The combined organic layers were washed with saturated aqueous NH 4 Cl (30 ml) and brine (30 ml), dried over MgSO 4, filtered and evaporated in vacuo. The resulting crude material was purified by recrystallization from EtOAc and hexane. The resulting product (5 mmol), 8-bromomethylquinoline (6 mmol), Al 2 O 3 (50 mmol), KOH (25 mmol) and dioxane (30 ml) were added to an over-dried 100 ml three-necked flask. The mixture was stirred for 8 h at 60 o C and then was filtered through a celite pad. The filtrate was washed with H 2 O (30 ml) and the organic layer was separated. The aqueous layer was extracted with EtOAc (2x15 ml). The combined organic layers were washed with brine (15 ml), dried over anhydrous Na 2 SO 4, filtrated and evaporated in vacuo. The resulting crude amide was purified by column chromatography on silica gel (eluent: hexane/etoac = 1/1). 2 Pokhrel, L.; kim, Y.; Nguyen, T.; Prior, A.; Lu, J.; Chang, K.; Hua, D. Bioorg. Med. Lett. 2012, 22, Sukata, K. Bull. Chem. Soc. Jpn. 1985, 58, 838. S2

4 IV. Typical Procedures for the Pd-Catalyzed Reaction of Aromatic Amides. To an oven-dried 5 ml screw-capped vial, N-(quinolone-8-ylmethyl)-2-(o-tolyl)acetamide (145 mg, 0.5 mmol), Pd(OAc) 2 (11.2 mg, 0.05 mmol), PhI(OAc) 2 (322 mg, 1.0 mmol), NaHCO 3 (84.0 mg, 1.0 mmol), toluene (2.0 ml) were added. The mixture was stirred for 16 h at 140 o C followed by cooling. The mixture was filtered through a celite pad and the filtrate concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluent: hexane/etoac = 10/1) to afford the desired lactone as a white solid. V. Spectroscopic Data. N-(quinoline-8-ylmethyl)-2-(o-tolyl)acetamide (1a) White solid. mp = C. R f 0.09 (Hexane/EtOAc = 1/3). 1 H NMR (CDCl 3, MHz) : 1.99 (s, 3H), 3.55 (s, 2H), 4.90 (d, J = 6.0 Hz, 2H), (m, 5H), 7.35 (dd, J = 16, 4.4 Hz, 1H), 7.45 (dd, J = 8.0, 7.2 Hz, 1H), 7.65 (d, J = 6.4 Hz, 1H), 7.71 (dd, J = 8.4, 1.2 Hz, 1H), 8.12 (dd, J = 8.4, 1.2 Hz, 1H) 8.54 (dd, J = 4.2, 1.6 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 21.4, 41.5, 43.9, 121.0, 126.5, 126.6, 127.6, 127.8, 128.4, 128.7, 129.2, 130.3, 134.9, 135.9, 136.6, 138.4, 146.7, 149.2, IR (neat): 3343 w, 3059 w, 2952 m, 2904 w, 2874 m, 2363 w, 1744 w, 1675 m, 1573 m, 1523 s, 1484 m, 1463 m, 1422 w, 1395 m, 1327 w, 1265 w, 1239 w, 1118 w, 1073 w, 1038 w, 1004 m, 825 w, 792 w, 767 s, 721 s, 703 s, 686 m. MS, m/z (relative intensity, %): 290 (M +, 27), 185 (13), 157 (69), 143 (12), 142 (100), 130 (15), 115 (15), 105 (13), 77 (15). Exact Mass (EI): Calcd for C 19 H 18 N 2 O , found (2-Methoxyphenyl)-N-(quinoline-8-ylmethyl)acetamide (1b) O MeO N H N White solid. mp = C. R f 0.17 (Hexane/EtoAc = 1/1). 1 H NMR (CDCl 3, MHz) : 3.42 (s, 3H), 3.53 (s, 2H), 4.90 (d, J = 6.0 Hz, 2H), 6.68 (d, J = 8.0 Hz, 1H), 6.87 (td, J = 14, 0.80 Hz, 1H), (m, 3H), 7.35 (dd, J = 8.2, 4.0 Hz, 1H), 7.42 (dd, J = 8.2, 7.6 Hz, 1H), (m, 1H), 7.70 (dd, J = 8.2, 1.2 Hz, 1H), 8.11 (dd, J = 8.2, 1.6 Hz, 1H), 8.67 (dd, J = 4.2, 1.6 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 38.9, 41.0, 54.7, 110.2, 120.6, 120.8, 123.6, 126.4, 127.2, 128.2, 128.5, 128.9, 131.2, 136.1, 136.3, 146.6, 149.1, 157.1, IR (neat): 3328 w, 2953 w, 2363 w, 1738 m, 1661 m, 1598 w, 1522 m, 1496 s, 1464 m, 1372 w, 1326 w, 1245 s, 1113 w, 1048 w, 1029 w, 825 w, 792 m, 755 m, 703 w. MS, m/z (relative intensity, %): 306 (M+, 29), 275 (14), 185 (28), 158 (12), 157 (97), 143 (14), 142 (100), 91 (15). Exact Mass (EI): Calcd for C 19 H 18 N 2 O , found S3

5 2-([1,1 -biphenyl]-2-yl)-n-(quinolin-8-ylmethyl)acetamide (1c) White solid. mp = C. R f 0.29 (Hexane/EtOAc = 1/1). 1 H NMR (CDCl 3, MHz) : 3.50 (s, 2H), 4.89 (d, J = 6.0 Hz, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 3H), 7.38 (dd, J = 8.4, 4.4 Hz, 1H), 7.47 (t, J = 7.6 Hz, 1H), 7.64 (d, J = 6.4 Hz, 1H), 7.75 (d, J = 8.4 Hz, 1H), 8.64 (d, J = 3.2 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 41.4, 41.5, 120.9, 126.4, 126.9, 127.1, 127.5, 127.7, 128.0, 128.3, 128.8, 129.3, 130.2, 130.8, 132.5, 135.8, 136.4, 140.7, 142.6, 146.7, 149.2, IR (ATR): 3253 w, 3017 w, 2945 w, 1668 s, 1595 w, 1577 w, 1518 m, 1500 m, 1479 m, 1438 w, 1414 w, 1362 w, 1334 w, 1317 w, 1263 w, 1247 w, 1222 m, 1163 w, 1135 w, 1105 w, 1073 w, 1009 w, 988 w, 917 w, 877 w, 829 m, 795 m, 768 s, 749 s, 706 s, 682 m, 660 m. MS, m/z (relative intensity, %): 353 (M + +1, 10), 352 (36), 185 (28), 165 (15), 158 (12), 157 (100), 143 (10), 142 (77). Exact Mass (EI): Calcd for C 24 H 20 N 2 O , found N-(quinoline-8-ylmethyl)-2-(m-tolyl)acetamide (1d) White solid. mp = C. R f 0.09 (Hexane/EtOAc = 1/1). 1 H NMR (CDCl 3, MHz) : 2.34 (s, 3H), 3.52 (s, 2H), 4.93 (d, J = 6.0 Hz, 2H), (m, 4H), 7.39 (dd, J = 8.2, 4.4 Hz, 1H), 7.46 (dd, J = 8.4, 7.2 Hz, 1H), 7.65 (d, J = 6.8 Hz, 1H), 7.73 (dd, J = 8.4, 0.80 Hz, 1H), 8.14 (dd, J = 8.4, 2.0 Hz, 1H), 8.65 (dd, J = 4.0, 2.0 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 21.2, 41.4, 43.7, 120.9, 126.3, 126.5, 127.4, 127.7, , 128.6, 129.0, 130.2, 134.8, 135.7, 136.4, 138.3, 146.6, 149.0, IR (neat): 3276 w, 3037 w, 2922 w, 2857 w, 2360 w, 2246 w, 1644 s, 1595 w, 1546 m, 1497 m, 1417 m, 1334 m, 1265 m, 1229 w, 1161 w, 1073 w, 1031 w, 909 w, 866 w, 822 m, 789 s, 758 m, 730 s, 710 m, 690 m. MS, m/z (relative intensity, %): 290 (M +, 15), 185 (16), 158 (10), 157 (96), 143 (12), 142 (100), 130 (17), 115 (15), 105 (15), 103 (11), 77 (19). Exact Mass (EI): Calcd for C 19 H 18 N 2 O , found (3-methoxyphenyl)-N-(quinolin-8-ylmethyl)acetamide (1e) White solid. mp = C. R f 0.46 (Hexane/EtOAc = 1/3). 1 H NMR (CDCl 3, MHz) : 3.53 (s, 2H), 3.67 (s, 3H), 4.93 (d, J = 6.0 Hz, 2H), 6.67 (s, 1H), 6.78 (d, J = 7.2 Hz, 1H), 6.80 (dd, J = 8.4, 2.8 Hz, 1H), S4

6 (m, 1H), 7.38 (dd, J = 8.4, 4.0 Hz, 1H), 7.46 (t, J = 8.0 Hz, 1H), 7.66 (d, J = 6.8 Hz, 1H), 7.73 (d, J = 8.0 Hz, 1H), 8.15 (dd, J = 8.4, 1.6 Hz, 1H), 8.66 (dd, J = 4.0, 1.6 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 41.5, 44.0, 55.0, 112.9, 114.7, 120.9, 121.9, 126.4, 127.5, 128.4, 129.1, 129.8, 135.8, , , 146.7, 149.2, 159.8, IR (ATR): 3297 w, 3067 w, 2915 w, 2836 w, 2371 w, 2320 w, 1648 s, 1613 m, 1581 m, 1546 s, 1493 m, 1453 w, 1420 m, 1352 w, 1336 w, 1297 m, 1267 s, 1226 m, 1154 m, 1076 w, 1051 m, 1029 m, 1010 w, 934 w, 864 w, 820 m, 787 s, 749 m, 702 m. MS, m/z (relative intensity, %): 307 (M + +1, 10), 306 (47), 185 (22), 158 (13), 157 (100), 143 (11), 142 (85). Exact Mass (EI): Calcd for C 19 H 18 N 2 O , found (2,4-dimethyoxyphenyl)-N-(quinolin-8-ylmethyl)acetamide (1f) White solid. mp = C. R f 0.17 (Hexane/EtOAc = 1/3). 1 H NMR (CDCl 3, MHz) : 3.42 (s, 3H), 3.47 (s, 2H), 3.80 (s, 3H), 4.92 (d, J = 6.0 Hz, 2H), 6.29 (d, J = 2.4 Hz, 1H), 6.42 (dd, J = 8.0, 2.4 Hz, 1H), (m, 1H), 7.39 (dd, J = 8.4, 4.4 Hz, 1H), 7.46 (t, J = 8.0 Hz, 1H), 7.66 (d, J = 6.8 Hz, 1H), 7.72 (d, J = 8.0 Hz, 1H), 8.14 (dd, J = 8.4, 1.6 Hz, 1H), 8.70 (dd, J = 4.4, 1.6 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 38.3, 41.1, 54.9, 55.4, 98.6, 104.3, 116.3, 120.9, 126.5, 127.3, 128.4, 129.0, 131.6, , , 146.8, 149.2, 158.2, 160.3, IR (ATR): 3263 w, 3061 w, 2989 w, 2935 w, 2821 w, 1641 m, 1618 m, 1590 m, 1555 s, 1507 s, 1453 m, 1416 m, 1375 w, 1350 w, 1329 m, 1290 w, 1261 m, 1248 m, 1210 s, 1156 s, 1122 s, 1042 s, 934 w, 909 w, 864 w, 819 s, 785 s, 754 s, 727 m, 664 m. MS, m/z (relative intensity, %): 337 (M + +1, 10), 336 (45), 185 (37), 178 (82), 157 (41), 151 (21), 143 (13), 142 (100), 121 (15). Exact Mass (EI): Calcd for C 20 H 20 N 2 O , found for (3,4-dimethoxyphenyl)-N-(quinolin-8-ylmethyl)acetamide (1g) White solid. mp = C. R f 0.20 (Hexane/EtOAc = 1/3). 1 H NMR (CDCl 3, MHz) : 3.50 (s, 2H), 3.63 (s, 3H), 3.88 (s, 3H), 4.93 (d, J = 6.4 Hz, 2H), 6.59 (d, J = 2.0 Hz, 1H), 6.71 (dd, J = 8.0, 2.0 Hz, 1H), 6.78 (d, J = 8.0 Hz, 1H), 7.38 (dd, J = 8.4, 4.0 Hz, 1H), 7.46 (t, J = 8.0 Hz, 1H), 7.67 (d, J = 6.8 Hz, 1H), 7.73 (d, J = 8.0 Hz, 1H), 8.14 (dd, J = 8.4, 1.6 Hz, 1H), 8.65 (dd, J = 4.0, 1.6 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 41.5, 43.6, 55.6, 55.9, 111.4, 112.4, 121.0, 121.8, 126.4, , , 128.4, 129.2, 136.0, 136.5, 146.8, 148.1, 149.1, 149.2, IR (ATR): 3317 w, 2933 w, 2829 w, 1736 w, 1635 s, 1593 m, 1544 m, 1513 s, 1468 m, 1420 m, 1374 w, 1340 w, 1315 m, 1258 s, 1230 s, 1150 s, 1027 s, 957 w, 930 w, 868 w, 824 w, 796 m, 783 s, 759 m, 701 m. MS, S5

7 m/z (relative intensity, %): 337 (13), 336 (100), 185 (15), 179 (11), 178 (100), 157 (29), 151 (14), 143 (10), 142 (83). Exact Mass (EI): Calcd for C 20 H 20 N 2 O , found for (naphthalen-1-yl)-N-(quinolin-8-ylmethyl)acetamide (1h) White Solide. mp = C. R f 0.17 (Hexane/EtOAc = 1/1). 1 H NMR (CDCl 3, MHz) : 3.99 (s, 2H), 4.83 (d, J = 6.0 Hz, 2H), (m, 1H), (m, 1H), (m, 2H), 7.40 (dd, J = 8.0, 6.8 Hz, 2H), 7.56 (d, J = 6.8 Hz, 1H), 7.63 (dd, J = 8.2, 1.6 Hz, 1H), 7.67 (d, J = 8.4 Hz, 1H), 7.77 (dd, J = 8.2, 4.0 Hz, 2H), 8.00 (dd, J = 8.2, 2.0 Hz, 1H), 8.20 (dd, J = 4.2, 1.6 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 41.5, 41.9, 120.8, 123.6, 125.4, 126.1, 127.3, 128.1, , , 128.9, 131.1, 131.9, 133.7, 135.5, 136.1, 146.3, 148.7, IR (neat): 3270 m, 3062 w, 3007 w, 2926 w, 2364 w, 1931 w, 1739 w, 1641 s, 1597 w, 1549 s, 1497 m, 1469 m, 1415 m, 1397 w, 1334 m, 1269 w, 1250 m, 1226 m, 1162 w, 1073 w, 1028 w, 984 w, 950 w, 911 w, 860 w, 822 m, 779 s, 758 m, 735 m. MS, m/z (relative intensity, %): 327 (10), 326 (43), 185 (39), 168 (17), 157 (44), 143 (13), 142 (100), 141(22), 115 (12). Exact Mass (EI): Calcd for C 22 H 18 N 2 O , found for methylbenzofuran-2(3H)-one (2a) White solid. mp = 86.9 C. R f 0.43 (Hexane/EtOAc = 10/1). 1 H NMR (CDCl 3, MHz) : 2.29 (s, 3H), 3.62 (s, 2H), (m, 2H), 7.20 (t, J = 7.6 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 18.8, 32.0, 107.9, 122.1, 124.8, 128.6, 134.7, 154.4, IR (ATR): 2918 w, 2359 w, 1796 s, 1618 m, 1602 m, 1491 w, 1453 m, 1389 w, 1328 w, 1261 m, 1226 m, 1199 m, 1158 w, 1112 s, 1069 w, 1003 m, 947 s, 897 w, 854 m, 827 m, 781 s, 760 m, 707 w. MS, m/z (relative intensity, %): 149 (M + +1, 10), 148 (100), 120 (55), 92 (38), 91 (49). Exact Mass (EI): Calcd for C 9 H 8 O , found methoxybenzofuran-2(3H)-one (2b) White solid. mp = 84.6 C. R f 0.14 (Hexane/EtOAc = 20/1). 1 H NMR (CDCl 3, MHz) : 3.65 (s, 2H), 3.86 (s, 3H), 6.67 (d, J = 8.0 Hz, 1H), 6.74 (d, J = 8.0 Hz, 1H), 7.27 (t, J = 8.0 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 30.9, 55.5, 103.6, 106.3, 110.4, 129.6, 155.4, 155.6, IR (ATR): 2952 w, 2849 w, 2364w, 1792 s, 1611 m, 1498 m, 1462 m, 1396 w, 1338 w, 1286 m, 1264 m, 1233 m, 1200 m, 1150 w, 1122 m, 1041 s, 950 m, 854 m, 766 s, 707 w. MS, m/z (relative intensity, %): 165 (M + +1, 10), 164 (100), 136 (72), 108 (24), 106 (36), 93 (17), 65 (18). Exact Mass (EI): Calcd for C 9 H 8 O , found S6

8 4-phenylbenzofuran-2-(3H)-one (2c) White solid. mp = 89.7 o C. R f 0.26 (Hexane/EtOAc = 10/1). 1 H NMR (CDCl 3, MHz) : 3.81 (s, 2H), 7.09 (d, J = 8.0 Hz, 1H), 7.23 (d, J = 8.0 Hz), (m, 6H). 13C NMR (CDCl 3, MHz) : 33.0, 109.6, 120.9, 124.2, 127.7, 127.9, 128.0, 128.8, 129.1, 138.8, 154.9, IR (ATR): 2994 w, 2360 w, 1810 s, 1613 w, 1594 w, 1572 w, 1502 w, 1475 w, 1455 w, 1428 m, 1380 w, 1327 w, 1282 w, 1253 w, 1223 m, 1198 m, 1179 w, 1157 w, 1129 m, 1057 s, 1026m, 1000 w, 964 w, 919 s, 849 m, 828 w, 793 m, 757 s, 703s. MS, m/z (relative intensity, %): 211 (M + +1, 15), 210 (100), 182 (34), 181 (33), 154 (15), 153 (33), 152 (19). Exact Mass (EI): Calcd for C 14 H 10 O , found methylbenzofuran-2(3H)-one (2d) White solid. R f 0.11 (Hexane/EtOAc = 20/1). 1 H NMR (CDCl 3, MHz) : 2.34 (s, 3H), 3.69 (s, 3H), (m, 1H), (m, 2H). 13 C NMR (CDCl 3, MHz) : 21.0, 33.1, 110.3, 122.9, 125.1, 129.1, 133.7, 152.6, Exact Mass (EI): Calcd for C 9 H 8 O , found methoxybenzofuran-2-(3H)-one (2e) White solid. R f 0.14 (Hexane/EtOAc = 20/1). 1 H NMR (CDCl 3, MHz) : 3.73 (s, 2H), 3.79 (s, 3H), (m, 2H), 7.02 (d, J = 8.4 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 33.6, 55.8, 110.1, 111.1, 113.7, 123.9, 148.6, 156.5, Exact Mass (EI): Calcd for C 9 H 8 O , found dimethoxybenzofuran-2(3H)-one (2f) White solid. R f 0.20 (Hexane/EtOAc = 10/1). 1 H NMR (CDCl 3, MHz) : 3.59 (s, 2H), 3.81 (s, 1H), 3.82 (s, 1H), 6.22 (d, J = 2.0 Hz, 1H), 6.32 (d, J = 2.0 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 30.7, 55.5, 55.8, 89.4, 94.2, 102.3, 155.8, 156.1, 161.6, Exact Mass (EI): Calcd for C 10 H 10 O , found S7

9 5,6-dimethoxybenzofuran-2(3H)-one (2g) R f 0.11 (Hexane/EtOAc = 5/1). 1 H NMR (CDCl 3, MHz) : 3.69 (s, 2H), 3.86 (s, 3H), 3.89 (s, 3H), 6.73 (s, 1H), 6.83 (s, 1H). 13 C NMR (CDCl 3, MHz) : 33.4, 56.3, 56.7, 96.1, 108.0, 113.1, 146.1, 148.7, 149.8, Exact Mass (EI): Calcd for C 10 H 10 O , found naphtha[2,1-b]furan-2(1h)-one (2h) White solid. R f 0.23 (Hexane/EtOAc = 20/1). 1 H NMR (CDCl 3, MHz) : 4.01 (s, 2H), 7.34 (d, J = 9.2 Hz, 2H), (m, 1H), (m, 1H), 7.63 (d, J = 8.0 Hz, 1H), 7.86 (dd, J = 8.4, 16.4 Hz, 2H). 13 C NMR (CDCl 3, MHz) : 32.3, 111.5, 116.6, 122.9, 124.9, 127.7, 129.2, 129.3, 129.8, 130.6, 152.3, Exact Mass (EI): Calcd for C 12 H 8 O , found oxo-2,3-dihydrobenzofuran-4-yl acetate (2i) White solid. mp = 91.4 C. 1 H NMR (CDCl 3, MHz) : 2.33 (s, 3H), 3.65 (s, 3H), 6.89 (d, J = 8.4 Hz, 1H), 7.01 (d, J = 8.0 Hz, 1H), 7.33 (t, J = 8.4, 8.0 Hz, 1H). 13 C NMR (CDCl 3, MHz) : 20.8, 31.7, 108.4, 116.2, 117.2, 130.0, 146.5, 155.3, 168.0, IR (ATR): 3084 w, 2979 w, 2322 w, 1806 s, 1764 m, 1631 m, 1610 w, 1491 w, 1460 m, 1388 w, 1372 w, 1328 w, 1267 w, 1241 w, 1197 s, 1112 s, 1047 m, 1019 s, 999 s, 901 m, 877 m, 850 m, 828 w, 795 m, 768 m, 714 m, 691 m. MS, m/z (relative intensity, %): 192 (M +, 33), 150 (100), 122 (79), 94 (13). Exact Mass (EI): Calcd for C 10 H 8 O , found (2-oxo-2-((quinolin-8-ylmethyl)amino)ethyl)naphthalene-2-yl acetate (5) O N H OAc N White solid. mp = C. R f 0.40 (Hexane/EtOAc = 1/1). 1 H NMR (CDCl 3, MHz) : 2.26 (s, 3H), 3.94 (s, 2H), 4.85 (d, J = 6.0 Hz, 2H), (m, 3H), (m, 2H), 7.45 (d, J = 6.8 Hz, 1H), 7.61 (d, H = 8.0 Hz, 1H), (m, 3H), 8.00 (dd, 1H), 8.30 (dd, 1H). 13 C NMR (CDCl 3, MHz) : 20.8, 34.5, 41.2, 120.7, 121.4, 121.7, 123.8, 125.7, 126.1, 126.9, 127.2, 128.0, 128.3, 128.6, 129.2, 131.7, 132.6, 135.7, 136.0, 146.3, 147.0, 148.8, , IR (ATR): 3276 w, 3065 w, 1756 m, 1635m, 1598 w, 1545 m, 1499 m, 1468 w, S8

10 1422 w, 1397 w,1364 w, 1334 w, 1204 s, 1184 s, 1064 w, 1011 m, 988 w, 906 w, 864 w, 813 m, 793 m, 760 m, 741 m. MS, m/z (relative intensity, %): 384 (M +, 18), 342 (15), 324 (20), 185 (25), 184 (30), 159 (45), 158 (19), 157 (62), 156 (16), 143 (19), 142 (100), 130 (16), 129 (16), 128 (23). Exact Mass (EI): Calcd for C 24 H 20 N 2 O , found S9

11 o-me SM abundance X : parts per Million : Proton S10

12 abundance o-me SM_13C X : parts per Million : Carbon S11

13 abundance MN-G-OMe_1H X : parts per Million : Proton S12

14 MN-G-OMe_13C abundance X : parts per Million : Carbon S13

15 TIG-069 GPC abundance X : parts per Million : Proton S14

16 TIG-069 a.r._13c abundance X : parts per Million : Carbon S15

17 MNG-para abundance X : parts per Million : Proton S16

18 MN-G-meta_13C abundance X : parts per Million : Carbon S17

19 abundance TIG-039 column X : parts per Million : Proton S18

20 TIG 3-Methoxy_13C abundance X : parts per Million : Carbon S19

21 TIG 2,4-Methoxy abundance X : parts per Million : Proton S20

22 Parameter file, TOPSPINVersion 3.2 (Thousands) X : parts per Million : 13C S21

23 abundance TIG 3,4-Methoxy GPC X : parts per Million : Proton S22

24 Parameter file, TOPSPINVersion 3.2 (Thousands) X : parts per Million : 13C S23

25 MN-G-naph_1H abundance X : parts per Million : Proton S24

26 abundance MN-G-naph_13C X : parts per Million : Carbon S25

27 abundance TI-050 f X : parts per Million : Proton S26

28 TI-Me CNMR_13C abundance X : parts per Million : Carbon S27

29 abundance MN-093 f X : parts per Million : Proton S28

30 abundance MN-093 column_13c X : parts per Million : Carbon S29

31 TI-055, 056 GPC abundance X : parts per Million : Proton S30

32 Parameter file, TOPSPINVersion 3.2 (Thousands) X : parts per Million : 13C S31

33 abundance TI-052 column X : parts per Million : Proton S32

34 TI-052 column 1_13C abundance X : parts per Million : Carbon S33

35 abundance m-meo Lactone X : parts per Million : Proton S34

36 TI-030 column2_13c abundance X : parts per Million : Carbon S35

37 TI-026 GPC 1 abundance X : parts per Million : Proton S36

38 abundance TI-026 GPC 1_13C X : parts per Million : Carbon S37

39 abundance TI column X : parts per Million : Proton S38

40 abundance TI column2_13c X : parts per Million : Carbon S39

41 abundance TI Lactone naphtyl X : parts per Million : Proton S40

42 TI Lactone naphtyl_13c abundance X : parts per Million : Carbon S41

43 abundance TIG AcO X : parts per Million : Proton S42

44 abundance TIG AcO X : parts per Million : Carbon S43

45 abundance TIG AcO X : parts per Million : Proton S44

46 abundance TIG OAc_13C X : parts per Million : Carbon S45