Supporting Information

Supporting Information Practical xidative Dearomatization of Phenols with Sodium Hypochlorite Pentahydrate Muhammet Uyanik, 1 Niiha Sasakura, 1 Mitsuyoshi Kuwahata, 2 Yasukazu Ejima, 2 and Kazuaki Ishihara* 1,3 1 Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 2 Kaneka Corporation, PVC & Chemical Division, 2-3-18 Nakanoshima, Kita-ku, saka 530-8288 3 Japan Science and Technology Agency (JST), CREST, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Received December 8, 2014; CL-141130; E-mail: ishihara@cc.nagoya-u.ac.jp) Copyright The Chemical Society of Japan

General Methods Infrared (IR) spectra were recorded on a JASC FT/IR 460 plus spectrometer. 1 H NMR spectra were measured on a JEL ECS-400 (400 MHz) spectrometer at ambient temperature. Data were recorded as follows: chemical shift in ppm from internal tetramethylsilane on the δ scale, multiplicity (s = singlet; d = doublet; t = triplet; q = quartet; m = multiplet), coupling constant (Hz), integration, and assignment. 13 C NMR spectra were measured on a JEL ECS-400 (100 MHz) spectrometer. Chemical shifts were recorded in ppm from the solvent resonance employed as the internal standard (deuterochloroform at 77.00 ppm, deuterodimethylsulfoxide at 39.50 ppm). For thin-layer chromatography (TLC) analysis throughout this work, Merck precoated TLC plates (silica gel 60 GF 254 0.25 mm) were used. The products were purified by column chromatography on silica gel (E. Merck Art. 9385) and NH-silica gel (FUJI SILYSIACHEMICAL LTD. DM1020). High-resolution mass spectral analysis (HRMS) was performed at Chemical Instrument Center, Nagoya University. In experiments that required dry solvents, dichloromethane and toluene were purchased from Wako Pure Chemical Industries, Ltd. as the anhydrous and stored over 4Å molecular sieves. Pure (deionized)-water and EtAc were purchased from Wako Pure Chemical Industries, Ltd., and used without further purification. ther solvents were purchased from Aldrich Chemical Co., Inc., Wako Pure Chemical Industries, Ltd. or Tokyo Chemical Industry Co., Ltd., and used without further purification. Aqueous sodium hypochlorite (ca. 10 wt%, ph ~13) and sodium hypochlorite pentahydrate (Wako, ph ~11) were purchased from Wako Pure Chemical Industries, Ltd. and used without further purification. Sodium hypochlorite pentahydrate (Kaneka, ph ~10.5) was provided from Kaneka Corporation and used without further purification. ther simple chemicals were analytical-grade and obtained commercially and used without further purification. S1

Starting Materials Substrates 1a, 1 1b, 2,3 1c, 1 1d g, 2,3 1h, 4 1j, 2,3 1k, 2,3 and 1l 5 are known compounds. 7, 9 and 11 are commercially available. Synthesis of 1i: H TBSCl (1.1 eq) Imidazole (1.2 eq) TBS ArB(H) 2 (1.5 eq) Pd(PPh 3 ) 4 (5 mol%) Cs 2 C 3 (2 eq) TBS TBAF (1.5 eq) H To a stirring mixture of 4-bromo-1-naphthol (S1, 3.85 g, 17.3 mmol) and imidazole (1.43 g, 21.0 mmol) in DMF (35.0 ml) was added tert-butyldimethylsilyl chloride (2.86 g, 19.0 mmol) at 0 ºC. The reaction mixture was allowed to room temperature. After 2 h, the resulting mixture was poured into H 2 and extracted with Et 2 (twice). The combined organic layers were washed with brine and dried over anhydrous MgS 4. The solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane EtAc = 50:1 to 30:1) to give S2 (5.46 g, 16.2 mmol, 94% yield). To a stirring mixture of S2 (3.37 g, 10.0 mmol), (4-methoxyphenyl)boronic acid (2.27 g, 15.0 mmol) and Cs 2 C 3 (6.52 g, 20.0 mmol) in degassed dioxane (50.0 ml) and H 2 (10.0 ml) was added Pd(PPh 3 ) 4 (0.580 g, 0.100 mmol) at room temperature. After stirring for 6 h at 80 C, the resulting mixture was poured into H 2 and extracted with EtAc (twice). combined organic layers were washed with brine and dried over anhydrous MgS 4. The solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane EtAc = 50:1 to 30:1) to give S3 (3.34 g, 9.15 mmol, 92% yield). DMF, RT, 2 h Dioxane/H 2 THF 80 ºC, 6 h 0 ºC to RT, 3.5 h Br Br Ar Ar S1 S2 S3 S4 C(Et) 3 (1.5 eq) (CH 3 ) 3 CC 2 H (0.5 eq) Toluene, Reflux, 24 h Et Ar S5 Et 1) 2 M HCl Et 2, RT 2) 2 M NaH THF/MeH, RT To a stirring mixture of S3 (3.34 g, 9.15 mmol) in THF (31.5 ml) was added tetrabutylammonium fluoride (13.7 ml, 13.7 mmol, 1.00 M in THF) at 0 ºC. The reaction mixture was allowed to room temperature. After stirring for 3.5 h, the resulting mixture was poured into H 2 and extracted with EtAc (twice). The combined organic layers were H Ar 1i H Ar = Me The S2

washed with brine and dried over anhydrous MgS 4. The solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane-etac = 20:1 to 10:1 to 4:1) to give S4 (1.98 g, 7.91 mmol, 86% yield). To a stirring mixture of S4 (1.98g, 7.91 mmol) and triethyl orthoacrylate (1.48 ml, 11.9 mmol) in toluene (20.0 ml) was added pivalic acid (0.409 g, 4.00 mmol) at room temperature and the resulting mixture was refluxed for 24 h. The resulting mixture was poured into 1 M NaH (ca. 8 ml) and extracted with Et 2 (twice). The combined organic layers were washed with brine and dried over anhydrous MgS 4. The solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane EtAc = 50:1) to give S5 (2.99 g, 7.91 mmol, >99% yield). To a stirring mixture of S5 (2.99 g, 7.91 mmol) in Et 2 (20.0 ml) was added 2 M HCl (ca. 10 ml) at room temperature. After stirring for overnight, the resulting mixture was extracted with EtAc (twice). The combined organic layers were washed with brine and dried over anhydrous Na 2 S 4. The solvents were removed in vacuo. To a stirring mixture of the crude product in THF (10.0 ml) and MeH (10.0 ml) was added 2 M NaH (ca. 10 ml) at room temperature. After stirring for 24 h, the resulting mixture was poured into 1 M HCl (ca. 30 ml) and extracted with EtAc (twice). The combined organic layers were washed with brine and dried over anhydrous MgS 4. The solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane EtAc = 4:1 to 1:2) to give 1i (1.51 g, 4.68 mmol, 59% yield for 2 steps). 3-(1-Hydroxy-4-(4-methoxyphenyl)naphthalen-2-yl)propanoic acid (1i): White solid; TLC, R f = 0.50 (hexane EtAc CHCl 3 = 1:2:1 with a few drops of AcH); IR (KBr) 3500 3200, 2930, 1711, 1607, 1575, 1514, 1391 cm -1 ; 1 H NMR (CDCl 3, 400 MHz) δ 2.89 (dd, J = 5.5, 7.8 Hz, 2H), 3.05 (dd, J = 5.5, 7.8 Hz, 2H), 3.88 (s, 3H), 7.00 (d, J = 8.7 Hz, 2H), 7.09 (s, 1H), 7.34 7.40 (m, 3H), 7.46 (dt, J = 1.4, 6.9 Hz, 1H), 7.82 (d, J = 7.8 Hz, 1H), 8.34 (d, J = 7.8 Hz, 1H); 13 C NMR (DMS-d 6, 100 MHz) δ 25.1, 34.1, 55.6, 113.7 (2C), 121.1, 122.2, 124.5, 124.9, 125.3, 125.4, 129.3, 130.5, 130.7, 130.8 (2C), 132.4, 148.7, 158.1, 174.2; HRMS (FAB+) m/z calcd for C 20 H 19 4 (M+H) 323.1278, found 323.1281. Synthesis of 3: S3

H H C 2 H LAH (2 eq) THF, 0 ºC to RT, 41 h H Ph 1b Ph 3 To a stirring mixture of LiAlH 4 (75.9 mg, 2.00 mmol) in THF (1.70 ml) was added 1b (292.3 mg, 1.00 mmol) in THF (1.70 ml) at 0 ºC. The reaction mixture was allowed to room temperature. After stirring for 2 h, the resulting mixture was cooled to 0 ºC and sequentially quenched by saturated aqueous Rochelle salt. The mixture was stirred over 20 min, and the resulting suspension was filtered through celite with EtAc. The filtrates were extracted with EtAc (twice). The combined organic layers were washed with brine and dried over anhydrous Na 2 S 4. The solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane EtAc = 10:1 to 2:1) to give 3 (179.7 g, 0.646 mmol, 65% yield). 3-(1-Hydroxy-4-phenylnaphthalen-2-yl)propanol (3): White solid; TLC, R f = 0.37 (hexane EtAc = 2:1); IR (KBr) 3500 3200, 2930, 1578, 1331 cm 1 ; 1 H NMR (CDCl 3, 400 MHz) δ 1.97 (tt, J = 6.0, 6.4 Hz, 2H), 2.03 (brs, 1H), 2.99 (t, J = 6.4 Hz, 2H), 3.70 (dt, J = 3.2, 6.0 Hz, 2H), 7.17 (s, 1H), 7.39 7.49 (m, 7H), 7.84 (d, J = 8.2 Hz, 1H), 7.87 (brs, 1H), 8.35 (d, J = 8.2 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 25.1, 31.4, 60.3, 119.2, 122.4, 125.0, 125.5, 125.6, 125.7, 126.8, 128.2 (2C), 129.7, 130.2 (2C), 131.5, 132.6, 140.9, 149.8; HRMS (FAB+) m/z calcd for C 19 H 19 2 (M+H) 279.1385, found 279.1387. Synthesis of 5: 1b TsH (0.4 eq) Toluene Reflux, 5 h Ph S6 NH 4 Ac (4 eq) DMF RT, 4 h H Ph S7 NH 2 LAH (5 eq) THF 0 ºC to RT, 2 h H H 2 N Ph S8 TBSCl (2 eq) Et 3 N (2.5 eq) TBS MsCl (1.5 eq) Et 3 N (2 eq) TBS TBAF (1.5 eq) H CH 2 Cl 2 0 ºC to RT, 12 h H 2 N Ph S9 CH 2 Cl 2 0 ºC to RT, 24 h HN Ph Ms S10 THF 0 ºC to RT, 5 h To a stirring mixture of 1b (2.92 g, 10.0 mmol) in toluene (50.0 ml) was added Ph 5 HN Ms S4

TsH H 2 (0.760 g, 4.00 mmol). After stirring for 5 h at 50 ºC, the resulting mixture was poured into H 2 and extracted with Et 2 (twice). The combined organic layers were washed with brine and dried over anhydrous MgS 4. The solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane EtAc = 50:1) to give S6 (2.33 g, 8.50 mmol, 85% yield). To a stirring mixture of S6 (2.33 g, 8.50 mmol) in DMF (17.0 ml) was added NH 4 Ac (2.62 g, 34.0 mmol). After stirring for 4 h at room temperature, the resulting mixture was poured into H 2 and extracted with EtAc (twice). The combined organic layers were washed with brine and dried over anhydrous Na 2 S 4. The solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane EtAc = 1:1) to give S7 (2.35 g, 8.1 mmol, 95% yield) as light yellow solid. To a stirring mixture of LiAlH 4 (1.23 g, 32.4 mmol) in THF (20.0 ml) was added a solution of S7 (2.35 g, 8.10 mmol) in THF (20.0 ml) at 0 ºC. The reaction mixture was allowed to room temperature. After stirring for 2 h at room temperature, the resulting mixture was cooled to 0 ºC and sequentially quenched by saturated aqueous Rochelle salt. The mixture was stirred over 20 min, and the resulting suspension was filtered through celite with EtAc. The filtrates were extracted with EtAc (twice). The combined organic layers were washed with brine and dried over anhydrous Na 2 S 4. The solvents were removed in vacuo. The residue was purified by flash column chromatography on NH-silica gel (eluent: hexane EtAc = 1:1) to give S8 (1.45 g, 5.30 mmol, 65% yield) as a white solid. To a stirring mixture of S8 (1.11 g, 4.00 mmol), triethylamine (1.09 ml, 8.00 mmol) and N,N-dimethyl-4-aminopyridine (0.490 g, 4.00 mmol) in CH 2 Cl 2 (20.0 ml) was added and tert-butyldimethylsilyl chloride (0.900 g, 6.00 mmol) at 0 ºC. After stirring for 12 h at room temperature, the mixture was poured into H 2 and extracted with CHCl 3 (twice). The combined organic layers were washed with brine and dried over anhydrous MgS 4. The solvents were removed in vacuo to give S9. To a stirring mixture of S9 and triethylamine (0.980 ml, 7.20 mmol) in CH 2 Cl 2 (30.0 ml) was added methanesulfonyl chloride (0.420 ml, 5.40 mmol) at 0 ºC. After stirring for 24 h at room temperature, the resulting mixture was quenched with 1 M HCl (ca. 10 ml) and extracted with CHCl 3 (twice). The combined organic layers were washed with brine and dried over anhydrous MgS 4. The solvents were removed in vacuo. The residue was purified by flash chromatography on silica gel (eluent: hexane EtAc = 4:1) to give S10 (1.18 g, 2.52 mmol, 63% yield for 2 steps). To a stirring mixture of S10 (1.18 g, 2.52 mmol) in THF was added tetrabutylammonium S5

fluoride (1.00 M in THF, 3.78 ml, 3.78 mmol) at 0 ºC. The reaction mixture was allowed to room temperature. After stirring for 5 h, the resulting mixture was poured into H 2 and extracted with EtAc (twice). The combined organic layers were washed with brine and dried over anhydrous MgS 4. The solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane EtAc = 4:1 to 2:1) to give 5 (0.960 g, 2.50 mmol, >99%). N-(3-(1-Hydroxy-4-phenylnaphthalen-2-yl)propyl)methanesulfonamide (5): White solid; TLC, R f = 0.44 (Hexane EtAc = 1:2); IR (KBr) 3376, 3284, 1576, 1292, 1212, 1136cm -1 ; 1 H NMR (DMS-d 6, 400 MHz) δ 1.82 (quin, J = 7.3 Hz, 2H), 2.84 (t, J = 7.3 Hz, 2H), 3.02 (dt, J = 5.5, 7.3 Hz, 2H), 3.38 (s, 3H), 7.03 (t, J = 5.5 Hz, 1H), 7.38 7.51 (m, 7H), 7.72 (d, J = 8.7 Hz, 1H), 8.29 (d, J = 8.7 Hz, 1H), 9.22 (brs, 1H); 13 C NMR (DMS-d 6, 100 MHz) δ 27.0, 30.3, 39.2, 42.4, 121.8, 122.4, 124.8, 125.0, 125.5 (2C), 126.9, 128.4 (2C), 129.8, 130.0 (2C), 130.6, 131.0, 140.4, 149.1; HRMS (FAB+) m/z calcd for C 20 H 22 N 3 SNa (M+Na) 378.1134, found 378.1135. S6

Table S1. xidation of phenols using sodium hypochlorite pentahydrate. a,b Entry Product NaCl H 2 Method Yield A: EtAc 1 1.1 equiv 78% 20 C, 12 h 2a B: EtAc/H 2 1.2 equiv 2 (28:1 v/v) 56% Br 0 C, 5 min 3 A: EtAc 1 equiv 20 C, 9 h 98% 4 A: EtAc 2b 1 equiv c 20 C, 4 h 99% 5 Ph B: EtAc/H 1.1 equiv 2 (20:1 v/v) 0 C, 5 min 96% 6 A: EtAc 1.1 equiv 20 C, 3 h 86% 7 t-bu A: EtAc 2c 1.1 equiv c 20 C, 1.5 h 86% 8 t-bu B: EtAc/H 1.1 equiv 2 (20:1 v/v) 0 C, 1 h 78% 9 A: EtAc 1.1 equiv 20 C, 7 h 99% 10 A: EtAc 2d 1.1 equiv c 20 C, 6 h 99% 11 Cl B: EtAc/H 1.1 equiv 2 (20:1 v/v) 0 C, 5 min 76% A: EtAc 12 1.1 equiv 91% 20 C, 7 h 2e B: EtAc/H 13 1.1 equiv 2 (20:1 v/v) 75% Br 0 C, 5 min A: EtAc 14 1 equiv 20% 20 C, 5 h 2f B: EtAc/H 15 1.1 equiv 2 (20:1 v/v) 80% 0 C, 5 min 16 2g 1.1 equiv Me 17 2h 1.1 equiv 3,5-(CF 3 ) 2 -C 6 H 3 B: EtAc/H 2 (20:1 v/v) 0 C, 5 min B: EtAc/H 2 (20:1 v/v) 0 C, 5 min 92% 99% S7

18 2i 1.1 equiv 19 1.1 equiv 2j 20 1.1 equiv Me 4-Me-C 6 H 4 21 2k 1.1 equiv 22 2l 1.1 equiv Bn B: EtAc/H 2 (20:1 v/v) 0 C, 5 min A: EtAc 20 C, 6 h B: EtAc/H 2 (20:1 v/v) 0 C, 5 min B: EtAc/H 2 (20:1 v/v) 0 C, 5 min B: EtAc/H 2 (20:1 v/v) 0 C, 5 min 96% 23% 78% 99% 99% 23 1 equiv 4 24 1.1 equiv 25 1 equiv N Ms 6 26 1.1 equiv 27 1 equiv 8 28 1.1 equiv 29 10 1.1 equiv 30 t-bu 1.1 equiv A: EtAc 20 C, 4 h B: EtAc/H 2 (30:1 v/v) 0 C, 3 h A: EtAc 20 C, 12 h B: EtAc/H 2 (70:1 v/v) 0 C, 30 min A: EtAc 0 C, 2 h B: EtAc/H 2 (6:1 v/v) RT, 3 h B: EtAc/H 2 (20:1 v/v) 0 C, 40 min A: EtAc 20 C, 4 h A: EtAc 31 12 1.1 equiv c 20 C, 3 h B: EtAc/H 32 1.1 equiv 2 (20:1 v/v) 0 C, 20 min a EtAc (0.02 M). Ph Ph H t-bu 26% 78% 51% 80% <10% 91% 98% 73% 82% 90% b Unless otherwise noted, NaCl 5H 2 (Wako) was used. c NaCl 5H 2 (Kaneka) was used. S8

Representative Procedure for Method A (Table 1, Entry 7 = Table S1, Entry 3) H Ph 1b C 2 H NaCl 5H 2 (1 equiv) EtAc (0.02 M) 20 ºC, 9 h Ph 2b To a stirring mixture of 1b (29.2 mg, 0.100 mmol) in EtAc (5.00 ml) was added NaCl 5H 2 (Wako, 16.8 mg, 0.100 mmol, 1 equiv) at 20 ºC. The reaction was monitored by TLC analysis. After 9 h, the resulting mixture was quenched by saturated aqueous Na 2 S 2 3 (ca. 5 ml) and saturated aqueous NaHC 3 (ca. 5 ml) at 0 ºC. The aqueous layer was separated and extracted with EtAc (twice). The combined organic layers were washed with brine. The combined organic layers were dried over anhydrous MgS 4, and then the solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane EtAc = 10:1 to 2:1) to give desired product 2b (28.5 mg, 0.982 mmol, 98% yield). Representative Procedure for Method B (Table 1, Entry 11 = Table S1, Entry 5) H Ph 1b C 2 H NaCl 5H 2 (1.1 equiv) EtAc (0.02 M)/H 2 (20:1 v/v) 0 ºC, 5 min Ph 2b For convenience, an aqueous solution of NaCl (10 wt%) was prepared from NaCl 5H 2 (Wako) and deionized-h 2 at 0 ºC immediately and stored at 0 C. To a stirring mixture of 1b (29.2 mg, 0.100 mmol) in EtAc (5.00 ml) and deionized-water (0.180 ml) was added 10 wt% aqueous NaCl (Wako, 70.0 µl, 0.110 mmol, 1.1 equiv) prepared above at 0 ºC. The reaction was monitored by TLC analysis. After 5 min, the resulting mixture was quenched by saturated aqueous Na 2 S 2 3 (ca. 5 ml) and saturated aqueous NaHC 3 (ca. 5 ml) at 0 ºC. The aqueous layer was separated and extracted with EtAc (twice). The combined organic layers were washed with brine. The combined organic layers were dried over anhydrous MgS 4, and then the solvents were removed in vacuo. The residue was purified by flash column chromatography on silica gel (eluent: hexane EtAc = 10:1 to 2:1) to give desired product 2b (27.9 mg, 0.961 mmol, 96% yield). S9

Characterization of Products 4 -Bromo-5,6,7,8 -tetrahydro-1 H,3H-spiro[furan-2,2 -naphthalene]-1,5(4h)-dione (2a): 1 White solid; TLC, R f = 0.57 (hexane EtAc = 1:1); 1 H NMR (CDCl 3, 400 MHz) δ 1.52 1.82 (m, 4H), 2.16 (ddd, J = 9.6, 11.0, 13.3 Hz, 1H), 2.21 2.56 (m, 5H), 2.56 (ddd, J = 2.3, 9.6, 17.6 Hz, 1H), 2.90 (ddd, J = 9.6, 11.0, 17.6 Hz, 1H), 6.62 (s, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 20.8, 22.0, 22.4, 26.2, 30.8, 31.1, 83.4, 124.0, 131.5, 135.7, 148.0, 175.9, 196.4. 4 -Phenylspiro-1 H,3H-spiro[furan-2,2 -naphthalene]-1,5(4h)-dione (2b): 2,3 White solid; TLC, R f = 0.47 (hexane EtAc = 1:1); 1 H NMR (CDCl 3, 400 MHz) δ 2.27 (ddd, J = 9.6, 11.0, 13.3 Hz, 1H), 2.54 (ddd, J = 2.3, 9.6, 13.3 Hz, 1H), 2.63 (ddd, J = 2.3, 9.6, 17.6 Hz, 1H), 2.93 (ddd, J = 9.6, 11.0, 17.6 Hz, 1H), 6.12 (s, 1H), 7.15 (d, J = 7.3 Hz, 1H), 7.34 7.50 (m, 6H), 7.56 (dt, J = 1.4, 7.3 Hz, 1H), 8.10 (dd, J = 1.4, 7.3 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 26.7, 31.5, 83.7, 127.4, 127.6, 128.2, 128.4, 128.6 (2C), 128.7 (2C), 128.9, 130.6, 135.3, 137.4, 137.6, 139.8, 176.3, 196.4. 7,9-Di-tert-butyl-1-oxaspiro[4.5]deca-7,9-diene-2,6-dione (2c): 1 Yellow solid; TLC, R f = 0.57 (hexane EtAc = 1:1); 1 H NMR (CDCl 3, 400 MHz) δ 1.15 (s, 9H), 1.23 (s, 9H), 1.98 2.03 (m, 1H), 2.30 2.36 (m, 1H), 2.51 (ddd, J = 1.4, 9.6, 17.8 Hz, 1H), 2.73 2.82 (m, 1H), 5.99 (d, J = 1.8 Hz, 1H), 6.89 (d, J = 1.8 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 26.0, 28.4 (3C), 29.0 (3C), 30.2, 34.4, 34.5, 85.5, 128.1, 135.8, 142.8, 143.7, 176.6, 199.0. 4 -Chloro-1 H,3H-spiro[furan-2,2 -naphthalene]-1,5(4h)-dione (2d): 2,3 White solid; TLC, R f = 0.43 (hexane EtAc = 1:1); 1 H NMR (CDCl 3, 400 MHz) δ 2.24 (ddd, J = 9.6, 11.0, 13.7 Hz, 1H), 2.46 (ddd, J = 2.3, 9.6, 13.7 Hz, 1H), 2.63 (ddd, J = 2.3, 9.6, 17.4 Hz, 1H), 2.91 (ddd, J = 9.6, 11.0, 17.4 Hz, 1H), 6.41 (s, 1H), 7.53 (dt, J = 1.8, 7.3 Hz, 1H), 7.74 7.80 (m, 2H), 8.07 (d, J = 7.3 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 26.5, 31.5, 83.4, 126.1, 127.3, 128.1, 129.1, 130.1, 131.8, 134.5, 135.8, 175.7, 194.7. 4 -Bromospiro[tetrahydrofuran-2,2 -(1 H-naphthaline)]-1,5-dione (2e): 2,3 White solid; TLC, R f = 0.43 (hexane EtAc = 1:1); 1 H NMR (CDCl 3, 400 MHz) δ 2.24 (ddd, J = 9.6, 11.0, 13.5 Hz, 1H), 2.46 (ddd, J = 2.3, 9.6, 13.5 Hz, 1H), 2.62 (ddd, J = 2.3, 9.6, 17.9 Hz, 1H), 2.90 (ddd, J = 9.6, 11.0, 17.9 Hz, 1H), 6.67 (s, 1H), 7.49 7.53 (m, 1H), 7.73 7.78 (m, 2H), 8.05 (d, J = 7.2 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 26.5, 31.2, 84.2, 122.5, 127.0, 128.0, 128.8, 130.1, 133.4, 135.1, 135.9, 175.7, 194.7. S10

1 H,3H-Spiro[furan-2,2 -naphthalene]-1,5(4h)-dione (2f): 2,3 White solid; TLC, R f = 0.46 (hexane EtAc CHCl 3 = 1:2:1); 1 H NMR (CDCl 3, 400 MHz) δ 2.18 (ddd, J = 9.6, 11.0, 13.5 Hz, 1H), 2.49 (ddd, J = 1.8, 9.6, 13.5 Hz, 1H), 2.60 (ddd, J = 1.8, 9.6, 17.6 Hz, 1H), 2.92 (ddd, J = 9.6, 11.0, 17.6 Hz, 1H), 6.21 (d, J = 10.4 Hz, 1H), 6.66 (d, J = 10.4 Hz, 1H), 7.26 (d, J = 8.0 Hz, 1H), 7.41 (t, J = 8.0 Hz, 1H), 7.62 (t, J = 8.0 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 26.5, 31.2, 83.4, 127.3, 127.8, 127.9, 127.9, 129.0, 132.3, 135.7, 136.8, 176.5, 196.5. 4 -Methyl-1 H,3H-spiro[furan-2,2 -naphthalene]-1,5(4h)-dione (2g): 2,3 Colorless amorphous; TLC, R f = 0.40 (hexane EtAc = 1:1); 1 H NMR (CDCl 3, 400 MHz) δ 2.11 2.21 (m, 1H), 2.21 (s, 3H), 2.41 (ddd, J = 1.8, 9.6, 13.8 Hz, 1H), 2.59 (ddd, J = 1.8, 9.6, 17.4 Hz, 1H), 2.91 (ddd, J = 9.6, 11.5, 17.4 Hz, 1H), 6.02 (s, 1H), 7.40 7.45 (m, 2H), 7.68 (dt, J = 0.9, 7.4 Hz, 1H), 8.05 (dd, J = 0.9, 7.4 Hz, 1H); 13 C NMR (CDCl 3, 125 MHz) δ 19.3, 26.8, 31.5, 83.5, 124.8, 127.3, 127.9, 128.7, 129.0, 133.1, 135.6, 137.9, 176.5, 196.8. 4 -(3,5-Bis(trifluoromethyl)phenyl)-1 H,3H-spiro[furan-2,2 -naphthalene]-1,5(4h)-dion e (2h): 4 White solid; TLC, R f = 0.66 (hexane EtAc = 1:1); 1 H NMR (CDCl 3, 400 MHz) δ 2.33 (ddd, J = 9.6, 11.5, 13.3 Hz, 1H), 2.55 (ddd, J = 1.8, 9.6, 13.3 Hz, 1H), 2.66 (ddd, J = 1.8, 9.6, 17.4 Hz, 1H), 2.94 (ddd, J = 9.6, 11.5, 17.4 Hz, 1H), 6.22 (s, 1H), 6.97 (dd, J = 0.9, 7.8 Hz, 1H), 7.51 (dt, J = 0.9, 7.4 Hz, 1H), 7.63 (dt, J = 1.4, 7.8 Hz, 1H), 7.84 (s, 2H), 7.98 (s, 1H), 8.15 (dd, J = 1.4, 7.4 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 26.4, 31.2, 83.3, 122.4, 123.0 (q, J C F = 271.7 Hz, 2C), 126.5, 127.4, 128.6, 129.0 (2C), 129.7, 132.2 (q, J C F = 33.4 Hz, 2C), 132.7, 135.7, 135.9, 137.4, 139.7, 175.9, 195.6 ; 19 F NMR (CDCl 3, 376 MHz) δ 62.7. 4 -(4-Methoxyphenyl)-1 H,3H-spiro[furan-2,2 -naphthalene]-1,5(4h)-dione (2i): White solid; TLC, R f = 0.52 (hexane EtAc = 1:1); IR (neat) 2954, 1787, 1692, 1608, 1511, 1452 cm -1 ; 1 H NMR (CDCl 3, 400 MHz) δ 2.27 (ddd, J = 9.6, 11.0, 13.3 Hz, 1H), 2.52 (ddd, J = 1.8, 9.6, 13.3 Hz, 1H), 2.63 (ddd, J = 1.8, 9.6, 17.4 Hz, 1H), 2.91 (ddd, J = 9.6, 11.0, 17.4 Hz, 1H), 3.87 (s, 3H), 6.09 (s, 1H), 7.00 (d, J = 8.7 Hz, 2H), 7.20 (d, J = 7.8 Hz, 1H), 7.28 (d, J = 8.7 Hz, 2H), 7.42 (t, J = 7.3 Hz, 1H), 7.57 (dt, J = 0.9, 7.8 Hz, 1H), 8.08 (dd, J = 0.9, 7.3 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 26.8, 31.5, 55.4, 83.8, 114.0 (2C), 127.3, 127.6, 128.1, 128.8, 129.8, 129.9 (2C), 130.1, 135.3, 137.6, 139.2, 159.8, 176.4, 196.6; HRMS (FAB+) m/z calcd for C 20 H 17 4 (M+H) 321.1121, found 321.1121. S11

6 -Methoxy-1 H,3H-spiro[furan-2,2 -naphthalene]-1,5(4h)-dione (2j): 2,3 White solid; TLC, R f = 0.27 (hexane EtAc = 1:1); 1 H NMR (CDCl 3, 400 MHz) δ 2.17 (ddd, J = 9.6, 11.0, 13.3 Hz, 1H), 2.40 (ddd, J = 2.2, 9.6, 13.3 Hz, 1H), 2.61 (ddd, J = 2.2, 9.6, 17.6 Hz, 1H), 2.95 (ddd, J = 9.6, 11.0, 17.6 Hz, 1H), 3.94 (s, 3H), 6.21 (d, J = 9.6 Hz, 1H), 6.60 (d, J = 9.6 Hz, 1H), 6.72 (d, J = 2.8 Hz, 1H), 6.91 (dd, J = 2.8, 8.7 Hz, 1H), 8.01 (d, J = 8.7 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 26.8, 31.6, 55.7, 82.8, 112.9, 114.2, 120.6, 127.9, 130.5, 133.3, 139.1, 165.6, 176.3, 194.8. 3 -((Benzyloxy)methyl)-1 H,3H-spiro[furan-2,2 -naphthalene]-1,5(4h)-dione (2k): 2,3 Colorless amorphous. TLC, R f = 0.43 (hexane EtAc = 1:1); 1 H NMR (CDCl 3, 400 MHz) δ 2.30 2.37 (m, 1H), 2.43 2.55 (m, 2H), 2.69 2.79 (m, 1H), 4.25 (d, J = 12.8 Hz, 1H), 4.36 (d, J = 12.8 Hz, 1H), 4.60 (s, 2H), 6.70 (s, 1H), 7.25 (d, J = 7.8 Hz, 1H) 7.30 7.40 (m, 6H), 7.62 (t, J = 7.8 Hz, 1H), 7.98 (d, J = 7.8 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 26.1, 30.4, 68.9, 73.3, 85.8, 124.6, 126.7, 127.7, 127.8(2C), 128.0 (2C), 128.5 (2C), 128.6 135.6, 136.8, 137.5, 140.0, 176.6, 196.9. 2 H,3H-Spiro[furan-2,1 -naphthalene]-2,5(4h)-dione (2l): 5 White solid; TLC, R f = 0.70 (hexane EtAc = 1:2); 1 H NMR (CDCl 3, 400 MHz) δ 2.11 2.20 (m, 1H), 2.62 2.70 (m, 2H), 2.81 2.91 (m, 1H), 6.18 (d, J = 9.6 Hz, 1H), 7.36 (dd, J = 1.6, 7.6 Hz, 1H), 7.41 (dt, J = 1.6, 7.6 Hz, 1H), 7.46 7.50 (m, 2H), 7.56 (d, J = 7.6 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 26.5, 35.7, 85.8, 122.4, 125.6, 129.0, 129.1, 129.7, 131.0, 140.4, 146.0, 176.4, 197.5. 4 -Phenyl-4,5-dihydro-1 H,3H-spiro[furan-2,2 -naphthalen]-1 -one (4): Pale yellow oil; TLC, R f = 0.49 (hexane EtAc = 4:1); IR (KBr) 1687, 1591, 1277, 1009 cm -1 ; 1 H NMR (CDCl 3, 400 MHz) δ 1.97 2.12 (m, 2H), 2.20 2.37 (m, 2H), 4.16 (q, J = 6.4, 14.2 Hz, 1H), 4.32 (dt, J = 5.5, 7.8 Hz, 1H), 6.11 (s, 1H), 7.09 (d, J = 7.8 Hz, 1H), 7.33 7.50 (m, 7H), 8.03 (dd, J = 1.4, 7.8 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 25.3, 36.6, 70.5, 84.4, 126.6, 127.5, 127.8, 128.0, 128.4 (2C), 128.9 (2C), 129.2, 134.3, 135.0, 137.5, 137.7, 138.6, 201.6; HRMS (FAB) m/z calcd for C 19 H 17 2 [M+H] + 277.1229, found 277.1234. 1 -(Methylsulfonyl)-4-phenyl-1H-spiro[naphthalene-2,2 -pyrrolidin]-1-one (6): White solid; TLC, R f = 0.32 (hexane EtAc = 2:1); IR (KBr) 1685, 1593, 1333, 1147cm -1 ; 1 H NMR (CDCl 3, 400 MHz) δ 2.04 2.37 (m, 4H), 3.03 (s, 3H), 3.68 3.78 (m, 2H), 6.27 (s, 1H), 7.16 (d, J = 7.8 Hz, 1H), 7.36 7.44 (m, 6H), 7.51 (t, J = 7.8 Hz, 1H), 8.10 (d, J = 7.8 Hz, 1H); S12

13 C NMR (CDCl 3, 100 MHz) δ 23.1, 39.7, 40.0, 49.4, 72.2, 126.9, 127.9 (2C), 128.0, 128.5 (2C), 128.7, 129.2 (2C), 134.9, 135.4, 136.6, 138.2, 138.5, 199.4; HRMS (FAB) m/z calcd for C 20 H 20 3 N 1 S 1 [M+H] + 354.1164, found 354.1162. 4-Hydroxy-2,4,6-trimethylcyclohexa-2,5-dien-1-one (8): 6 Colorless oil; TLC, R f = 0.22 (hexane EtAc = 4:1); 1 H NMR (CDCl 3, 400 MHz) δ 1.43 (s, 3H), 1.86 (s, 6H), 2.22 (brs, 1H), 6.63 (s, 2H); 13 C NMR (CDCl 3, 100 MHz) δ 15.8 (2C), 27.0, 67.1, 133.3 (2C), 147.4 (2C), 186.8. 3,5-Di-tert-butylcyclohexa-3,5-diene-1,2-dione (10): 7 Dark green solid; TLC, R f = 0.60 (hexane EtAc = 4:1); 1 H NMR (CDCl 3, 400 MHz) δ 1.23 (s, 9H), 1.27 (s, 9H), 6.22 (s, 1H), 6.94 (s, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 27.8 (3C), 29.2 (3C), 35.4, 36.0, 122.0, 133.4, 149.9, 163.3, 180.0, 181.1. 2,3,5-Trimethylcyclohexa-2,5-diene-1,4-dione (12): 7 Pale yellow oil; TLC, R f = 0.63 (hexane EtAc = 4:1); 1 H NMR (CDCl 3, 400 MHz) δ 2.01 (s, 3H), 2.03 2.04 (m, 6H), 6.56 (m, 1H); 13 C NMR (CDCl 3, 100 MHz) δ 12.0, 12.3, 15.8, 133.0, 140.7, 140.8, 145.3, 187.4, 187.8. References 1. M. Uyanik, T. Yasui, K. Ishihara, Angew. Chem. Int. Ed. 2013, 52, 9215. 2. M. Uyanik, T. Yasui, K. Ishihara, Angew. Chem. Int. Ed. 2010, 49, 2175. 3. M. Uyanik, T. Yasui, K. Ishihara, Tetrahedron 2010, 66, 5841. 4. M. Uyanik, N. Sasakura, E. Kaneko, K. hori, K. Ishihara, Chem. Lett. 2014, 44, 179. 5. N. Takenaga, T. Uchiyama, D. Kato, H. Fujioka, T. Dohi, Y. Kita, Heterocycles 2011, 82, 1327. 6. A.-M. Abu-Elfotoh, K. Tsuzuki, T. B. Nguyen, S. Chanthamath, K. Shibatomi, S. Iwasa, Tetrahedron 2013, 69, 8612. 7. M. C. Carreño, M. González-López, A. Urbano, Angew. Chem. Int. Ed. 2006, 45, 2737. S13

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 8.4010 8.3804 7.9440 7.9142 7.8901 7.8466 7.6473 7.6290 7.6072 7.5476 7.5339 7.5305 7.5133 7.5098 7.4869 7.4835 7.4697 7.4663 7.4491 7.4468 7.2910 7.2601 7.1376 3.5247 3.5075 3.4892 3.4720 3.1100 3.0963 3.0905 3.0802 3.0126 2.9485 2.9382 2.9336 2.9187 2.0516 1.2520 1.2371 1.2257 1.2085 1.1913 0.1455 0.0298 0.0000 0.0092 0.0309 0.1501 X : parts per Million : 1H S14

S15 220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0 10.0 20.0 40.1197 39.9100 39.7098 39.5000 39.2902 39.0805 38.8707 34.2083 25.2649 142.9692 131.0129 130.8985 130.6887 130.5171 130.3645 130.2882 130.0308 127.5137 126.5126 125.5591 125.1586 124.8059 124.0050 122.6987 122.0885 121.3925 150.4920 174.4429 X : parts per Million : 13C

S16 200.0 180.0 160.0 140.0 120.0 100.0 80.0 60.0 40.0 20.0 0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0 180.0 200.0 62.5660 X : parts per Million : 19F

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 8.3483 8.3289 7.8260 7.8054 7.5190 7.4938 7.4904 7.4766 7.4732 7.4697 7.4560 7.4526 7.4136 7.4102 7.3964 7.3896 7.3850 7.3735 7.3678 7.3609 7.2979 7.2899 7.2601 7.1055 7.0287 7.0207 7.0161 7.0047 6.9989 6.9921 4.1318 4.1146 4.0665 3.9267 3.9187 3.8889 3.7068 3.5189 3.5018 3.4834 3.4663 3.0814 3.0676 3.0619 3.0516 2.9817 2.9141 2.9027 2.8981 2.8843 2.1787 2.1077 2.0504 1.2772 1.2600 1.2520 1.2417 1.2257 1.2085 1.1902 0.1466 0.0378 0.0309 0.0080 0.0000 0.0080 0.0298 0.1489 X : parts per Million : 1H S17

S18 220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0 10.0 20.0 40.1293 39.9195 39.7098 39.5000 39.2902 39.0805 38.8707 34.3037 25.3602 55.1748 132.5479 130.9938 130.8603 130.7173 129.4873 125.6068 125.5210 125.1396 124.7200 122.3459 121.2971 113.8411 148.8807 158.2913 174.4047 X : parts per Million : 13C

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 1.0 8.3598 8.3392 7.9073 7.8718 7.8500 7.8294 7.6771 7.6576 7.5877 7.5499 7.4949 7.4881 7.4743 7.4686 7.4594 7.4388 7.4205 7.4067 7.3999 7.3930 7.3884 7.3850 7.3758 7.3689 7.2853 7.2475 7.2017 7.1650 6.9692 3.7217 3.7080 3.6999 3.6862 3.5098 3.4926 3.4743 3.4571 3.0596 3.0356 3.0012 2.9851 2.9680 2.0321 2.0023 1.9874 1.9702 1.9554 1.9405 1.6163 1.2543 1.2280 1.2108 1.1936 0.0000 X : parts per Million : 1H S19

S20 220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0 10.0 20.0 25.0747 31.3961 60.3336 77.3242 77.0000 76.6854 140.9008 132.5866 131.4806 130.2220 129.6881 128.1816 126.7800 125.6645 125.5692 125.4643 124.9971 122.4132 119.2191 149.8156 X : parts per Million : 13C

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 1.0 9.2206 8.3065 8.2859 7.7532 7.7315 7.5333 7.5127 7.4943 7.4749 7.4474 7.4290 7.4210 7.4050 7.3981 7.3890 7.3844 7.3809 7.2332 7.0396 7.0258 7.0121 3.7497 3.6054 3.5917 3.5882 3.5779 3.5756 3.3774 3.3534 3.0475 3.0304 3.0143 2.9971 2.8918 2.8574 2.8391 2.8184 2.5000 1.8562 1.8379 1.8196 1.8001 1.7818 1.7612 1.7566 1.7497 1.7451 1.7405 1.7360 X : parts per Million : 1H S21

S22 220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0 10.0 20.0 42.3794 40.1293 39.9195 39.7098 39.5000 39.2998 39.2330 39.0900 38.8803 30.2991 26.9906 140.3472 130.9747 130.5361 129.9641 129.8020 128.3813 126.8653 125.5210 125.0156 124.7486 122.3650 121.7453 149.0427 X : parts per Million : 13C

S23 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 1.0 2.0 8.1628 8.1593 8.1444 8.1410 7.9818 7.9451 7.8409 7.8088 7.7687 7.6542 7.6507 7.6347 7.6313 7.6164 7.6118 7.5327 7.5305 7.5144 7.5110 7.4949 7.4927 7.2945 7.2647 7.0001 6.9829 6.9634 6.2647 6.2418 6.2338 3.9943 3.9886 3.9806 3.9737 3.5075 3.4903 3.4731 3.4548 2.9909 2.9668 2.9622 2.9462 2.9382 2.9233 2.9187 2.8947 2.6965 2.6919 2.6736 2.6678 2.6530 2.6472 2.6289 2.6232 2.5877 2.5819 2.5636 2.5579 2.5544 2.5487 2.5304 2.5247 2.3712 2.3471 2.3425 2.3379 2.3185 2.3139 2.3093 2.2853 2.2749 2.1764 1.6999 1.6633 1.6197 1.6060 1.5773 1.4330 1.4055 1.3666 1.3482 1.3311 1.2795 1.2543 1.2291 1.2108 1.1936 0.9061 0.8935 0.8878 0.8797 0.8694 0.8522 0.8442 0.8293 0.8064 0.7354 0.1466 0.0722 0.0309 0.0080 0.0000 0.0080 0.0309 X : parts per Million : 1H

S24 220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0 10.0 20.0 26.4191 31.2435 77.3146 77.0000 76.6854 83.3119 139.7089 137.4302 135.9046 135.6853 132.7105 132.3673 132.0336 131.6808 129.6785 129.0397 128.6202 127.4570 127.0756 126.5226 124.3583 122.4132 121.6409 118.9235 175.9594 195.5720 X : parts per Million : 13C

S25 200.0 180.0 160.0 140.0 120.0 100.0 80.0 60.0 40.0 20.0 0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0 180.0 200.0 62.6889 X : parts per Million : 19F

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 8.0940 8.0917 8.0757 8.0723 7.5877 7.5843 7.5683 7.5648 7.5488 7.5453 7.4881 7.4411 7.4228 7.4045 7.3586 7.3002 7.2933 7.2888 7.2762 7.2716 7.2636 7.2086 7.1891 7.0677 7.0012 6.9944 6.9898 6.9726 6.2991 6.0929 5.8832 4.6163 4.2097 4.0505 3.9485 3.9107 3.9038 3.8729 3.8408 3.8351 3.8259 3.6908 2.9668 2.9428 2.9393 2.9233 2.9153 2.8992 2.8947 2.8706 2.6621 2.6564 2.6381 2.6323 2.6174 2.6129 2.5945 2.5888 2.5522 2.5476 2.5281 2.5224 2.5189 2.5132 2.4949 2.4903 2.3105 2.2864 2.2818 2.2772 2.2578 2.2532 2.2486 2.2245 2.0481 1.6071 1.2543 0.8797 0.8614 0.0722 0.0080 0.0000 X : parts per Million : 1H S26

S27 220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0 10.0 20.0 26.7623 31.4819 55.3565 77.3242 77.0000 76.6854 83.8172 130.1267 129.9455 129.8216 128.8014 128.0958 127.6191 127.3426 113.9846 139.3752 137.6209 135.2754 159.6648 176.4361 196.5064 X : parts per Million : 13C

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 1.0 8.0448 8.0413 8.0253 8.0219 7.4995 7.4961 7.4801 7.4766 7.4617 7.4571 7.4503 7.4445 7.4400 7.4285 7.4251 7.4102 7.4045 7.3999 7.3953 7.3873 7.3735 7.3712 7.3586 7.3541 7.3426 7.3380 7.3346 7.2590 7.1032 7.0837 6.1089 4.3494 4.3357 4.3300 4.3162 4.3105 4.2967 4.1879 4.1719 4.1524 4.1352 2.3666 2.3563 2.3494 2.3379 2.3276 2.3185 2.3070 2.2933 2.2749 2.2635 2.2555 2.2452 2.2383 2.2280 2.2200 2.2097 2.1959 2.1203 2.1054 2.1008 2.0882 2.0836 2.0710 2.0573 2.0539 2.0390 2.0344 2.0218 2.0103 2.0023 1.9909 1.9714 1.5980 1.2852 1.2543 1.2211 0.0000 X : parts per Million : 1H S28

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 8.1055 8.0860 7.5259 7.5064 7.4881 7.4434 7.4274 7.4102 7.3758 7.3575 7.2601 7.1662 7.1467 6.2658 3.7836 3.7641 3.7458 3.7228 3.7045 3.6839 3.0264 2.3379 2.3231 2.3116 2.2944 2.2784 2.2623 2.2486 2.2200 2.2085 2.1936 2.1799 2.1638 2.1157 2.1008 2.0882 2.0722 2.0596 2.0436 1.5877 1.2761 1.2577 0.0000 X : parts per Million : 1H S30