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1 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 Kaneka Corporation, PVC & Chemical Division, Nakanoshima, Kita-ku, saka Japan Science and Technology Agency (JST), CREST, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi (Received December 8, 2014; CL ; ishihara@cc.nagoya-u.ac.jp) Copyright The Chemical Society of Japan

2 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 ppm, deuterodimethylsulfoxide at ppm). For thin-layer chromatography (TLC) analysis throughout this work, Merck precoated TLC plates (silica gel 60 GF 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

3 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, 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

4 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) , 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), (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, (2C), 121.1, 122.2, 124.5, 124.9, 125.3, 125.4, 129.3, 130.5, 130.7, (2C), 132.4, 148.7, 158.1, 174.2; HRMS (FAB+) m/z calcd for C 20 H 19 4 (M+H) , found Synthesis of 3: S3

5 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, 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) , 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), (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, (2C), 129.7, (2C), 131.5, 132.6, 140.9, 149.8; HRMS (FAB+) m/z calcd for C 19 H 19 2 (M+H) , found 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

6 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

7 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), (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, (2C), 126.9, (2C), 129.8, (2C), 130.6, 131.0, 140.4, 149.1; HRMS (FAB+) m/z calcd for C 20 H 22 N 3 SNa (M+Na) , found S6

8 Table S1. xidation of phenols using sodium hypochlorite pentahydrate. a,b Entry Product NaCl H 2 Method Yield A: EtAc equiv 78% 20 C, 12 h 2a B: EtAc/H 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 equiv 91% 20 C, 7 h 2e B: EtAc/H 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 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

9 18 2i 1.1 equiv equiv 2j equiv Me 4-Me-C 6 H k 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 equiv 25 1 equiv N Ms equiv 27 1 equiv equiv 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 equiv c 20 C, 3 h B: EtAc/H 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

10 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, mmol) in EtAc (5.00 ml) was added NaCl 5H 2 (Wako, 16.8 mg, 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, 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, mmol) in EtAc (5.00 ml) and deionized-water (0.180 ml) was added 10 wt% aqueous NaCl (Wako, 70.0 µl, 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, mmol, 96% yield). S9

11 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 (m, 4H), 2.16 (ddd, J = 9.6, 11.0, 13.3 Hz, 1H), (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, 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), (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, (2C), (2C), 128.9, 130.6, 135.3, 137.4, 137.6, 139.8, 176.3, ,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), (m, 1H), (m, 1H), 2.51 (ddd, J = 1.4, 9.6, 17.8 Hz, 1H), (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, 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), (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, 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), (m, 1H), (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, S10

12 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, 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 (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), (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, (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, (q, J C F = Hz, 2C), 126.5, 127.4, 128.6, (2C), 129.7, (q, J C F = 33.4 Hz, 2C), 132.7, 135.7, 135.9, 137.4, 139.7, 175.9, ; 19 F NMR (CDCl 3, 376 MHz) δ (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, (2C), 127.3, 127.6, 128.1, 128.8, 129.8, (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) , found S11

13 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, ((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 (m, 1H), (m, 2H), (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) (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), (2C), (2C), , 136.8, 137.5, 140.0, 176.6, 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 (m, 1H), (m, 2H), (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), (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, 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 (m, 2H), (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), (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, (2C), (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] , found (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 (m, 4H), 3.03 (s, 3H), (m, 2H), 6.27 (s, 1H), 7.16 (d, J = 7.8 Hz, 1H), (m, 6H), 7.51 (t, J = 7.8 Hz, 1H), 8.10 (d, J = 7.8 Hz, 1H); S12

14 13 C NMR (CDCl 3, 100 MHz) δ 23.1, 39.7, 40.0, 49.4, 72.2, 126.9, (2C), 128.0, (2C), 128.7, (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] , found 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, (2C), (2C), ,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, ,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), (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, References 1. M. Uyanik, T. Yasui, K. Ishihara, Angew. Chem. Int. Ed. 2013, 52, M. Uyanik, T. Yasui, K. Ishihara, Angew. Chem. Int. Ed. 2010, 49, M. Uyanik, T. Yasui, K. Ishihara, Tetrahedron 2010, 66, M. Uyanik, N. Sasakura, E. Kaneko, K. hori, K. Ishihara, Chem. Lett. 2014, 44, N. Takenaga, T. Uchiyama, D. Kato, H. Fujioka, T. Dohi, Y. Kita, Heterocycles 2011, 82, A.-M. Abu-Elfotoh, K. Tsuzuki, T. B. Nguyen, S. Chanthamath, K. Shibatomi, S. Iwasa, Tetrahedron 2013, 69, M. C. Carreño, M. González-López, A. Urbano, Angew. Chem. Int. Ed. 2006, 45, S13

15 X : parts per Million : 1H S14

16 S X : parts per Million : 13C

17 S X : parts per Million : 19F

18 X : parts per Million : 1H S17

19 S X : parts per Million : 13C

20 X : parts per Million : 1H S19

21 S X : parts per Million : 13C

22 X : parts per Million : 1H S21

23 S X : parts per Million : 13C

24 S X : parts per Million : 1H

25 S X : parts per Million : 13C

26 S X : parts per Million : 19F

27 X : parts per Million : 1H S26

28 S X : parts per Million : 13C

29 X : parts per Million : 1H S28

30 S X : parts per Million : 13C

31 X : parts per Million : 1H S30

32 S X : parts per Million : 13C