Supporting Information

Transcript

1 Supporting Information Transition-metal-free Ring Expansion Reactions of Indene-1,3-dione: Synthesis of Functionalized Benzoannulated Seven-Membered Ring Compounds Qiyi Yao, Lingkai Kong, Mengdan Wang, Yang Yuan, Ruizhuo Sun, Yanzhong Li* Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai , China. Fax: (+86) , Table of Contents 1. General Details Preparation of Acetyenic Ketones Synthesis of Compounds Synthesis of Compounds Gram sacle Synthesis of Compound 6a Copies of Spectra of New Products X-ray Crystallography of Compound 5a X-ray Crystallography of Compound 6a S1

2 1. General Details. All reactions were performed in flame-dried glassware under N 2, and the workup was carried out in N 2, unless otherwise noted. Dimethyl sulfoxide (DMS) was dried and distilled from calcium hydride. Column chromatographic purification of products was carried out using silica gel (200~300 mesh). The reagents were used without further purification. 1 H NMR spectra was recorded at 400 MHz, 13 C NMR spectra was recorded at 100 MHz, and in CDCl 3 (containing 0.03% TMS) solutions. 1 H NMR spectra was recorded with tetramethylsilane (δ = 0.00 ppm) as internal reference; 13 C NMR spectra was recorded with CDCl 3 (δ = ppm) as internal reference. High-resolution mass spectra were performed on a mass spectrometer with a TF (for EI or ESI) or FT-ICR (for MALDI) analyzer. Single crystal X-ray diffraction data was collected in Bruker SMARTAPEX diffractiometers with molybdenum cathodes. 2. Preparation of Acetyenic Ketones General procedure for the preparation of Acetyenic Ketones To a solution of alkyne (12 mmol) in anhydrous THF (30 ml), n-buli (2.5M, 10 mmol, 4 ml) was added at -78 o C. The resulting mixture was stirred at -78 o C for 40 min, then the aldehyde (10 mmol) was added and the reaction temperature was raised to room temperature till aldehyde disappeared by TLC analysis. The resulting mixture was quenched with a saturated solution of NH 4 Cl and extracted with ethyl acetate (20 ml 3). The combined organic layers were washed with brine and dried over anhydrous Na 2 S 4, filtered, and concentrated under reduced pressure. Purification by column chromatography with petroleum ether/ethyl acetate = 10:1-5:1 as the eluent afforded the substituted alkynol. S2

3 To a solution of substituted alkynol (10 mmol) in DMS (20 ml) in round-bottom flask, IBX (12 mmol, 3.36 g) was added at room temperature. The reaction was stirred in air until the full conversion of substituted alkynol monitored by thin-layer chromatography. The resulting mixture was quenched with water (20 ml) and filtered. Then the filtrate was extracted with ethyl acetate (20 ml 3). The organic layers was combined, washed with brine, dried over anhydrous Na 2 S 4, filtered and concentrated under reduced pressure. Purification by column chromatography with petroleum ether/ethyl acetate = 20:1-10:1 as the eluent afforded the acetyenic ketones. 3. Synthesis of Compounds 3 In a Schlenk tube 1-phenyl-3-(p-tolyl)prop-2-yn-1-one 1a (0.20 mmol, 44.1 mg), Cs 2 C 3 (0.6 mmol, mg), DMS (5.0 ml) and 1H-indene-1,3(2H)-dione 2a (0.28 mmol, 40.9 mg) was stirred at 110 o C under N 2. After the reaction was completed as monitored by thin-layer chromatography, the reaction mixture was then quenched by water, and the water layers were extracted with ethyl acetate (10 ml 3). The combined organic layers were washed with brine, dried over anhydrous Na 2 S 4, filtered, and concentrated under reduced pressure. Purification by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1) afforded desired compound 3a. S3

4 8-benzoyl-9-hydroxy-7-(p-tolyl)-5H-benzo[7]annulen-5-one (3a): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 61.6 mg (84% yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.17 (s, 3H), 6.55 (s, 1H), (m, 2H), (m, 2H), (m, 2H), (m, 3H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); δ 20.72, , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 25 H 18 Na 3 [M+Na] + : ; found benzoyl-9-hydroxy-7-(4-methoxyphenyl)-5H-benzo[7]annulen-5-one (3b): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 60.8 mg (79% yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 3.67 (s, 3H), (m, 2H), 6.56 (s, 1H), (m, 2H), ,16 (m, 2H), (m, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); δ 55.11, , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 25 H 18 Na 4 [M+Na] + : ; found benzoyl-9-hydroxy-7-phenyl-5H-benzo[7]annulen-5-one (3c): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 57.1 mg (81% yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ S4

5 6.56 (s, 1H), 7.02 (brs, 4H), ,15 (m, 2H), (m, 4H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); δ , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 24 H 16 Na 3 [M+Na] + : ; found benzoyl-7-(4-chlorophenyl)-9-hydroxy-5H-benzo[7]annulen-5-one (3d): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 60.5 mg (78% yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.50 (s, 1H), (m, 4H), ,19 (m, 2H), ,31 (m, 3H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 24 H 16 Cl 3 [M+H] + : ; found benzoyl-9-hydroxy-7-methyl-5H-benzo[7]annulen-5-one (3e): Brown solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 27.3 mg (47% yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.69 (s, 3H), 4.82 (s, 2H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), 8.03 (d, J = 8.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 19 H 14 Na 3 [M+H] + : ; found S5

6 9-hydroxy-7-phenyl-8-(3,4,5-trimethoxybenzoyl)-5H-benzo[7]annulen-5-one (3f): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 5:1), 70.7 mg (80% yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 3.74 (s, 6H), 3.80 (s, 3H), 6.51 (brs, 2H), 6.55 (s, 1H), (m, 5H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); δ 56.07, 60.70, , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 27 H 22 Na 6 [M+Na] + : ; found hydroxy-8-(4-methoxybenzoyl)-7-phenyl-5H-benzo[7]annulen-5-one (3g): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 55.4 mg (73% yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 3.76 (s, 3H), 6.58 (s, 1H), (m, 2H), (m, 5H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); δ 55.23, , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 25 H 18 Na 4 [M+Na] + : ; found hydroxy-8-(4-methylbenzoyl)-7-phenyl-5H-benzo[7]annulen-5-one (3h): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 62.6 mg (85% yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.26 (s, 3H), 6.57 (s, 1H), (m, 2H), 7.04 (brs, 4H), ,27 (m, 3H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); δ 21.22, , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 25 H 19 3 [M+H] + : ; found S6

7 8-(4-fluorobenzoyl)-9-hydroxy-7-phenyl-5H-benzo[7]annulen-5-one (3i): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 53.9 mg (73% yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.50 (s, 1H), (m, 2H), (m, 5H), ,28 (m, 2H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , (J = 21.8 Hz), , , (J = 10.3 Hz), , (J = 9.2 Hz), , , , , (J = 36.4 Hz), , , , , , HRMS (ESI) calcd for C 24 H 16 F 3 [M+H] + : ; found (4-chlorobenzoyl)-9-hydroxy-7-phenyl-5H-benzo[7]annulen-5-one (3j): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 66.8 mg (86 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.57 (s, 1H), ,12 (m, 7H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); δ , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 24 H 16 Cl 3 [M+H] + : ; found (4-bromobenzoyl)-9-hydroxy-7-phenyl-5H-benzo[7]annulen-5-one (3k): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 62.7 mg (73 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.56 (s, 1H), ,08 (m, 4H), (m, 2H), (m, 3H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , S7

8 131.32, , , , , , , , , , HRMS (ESI) calcd for C 24 H 15 BrNa 3 [M+Na] + : ; found (1-naphthoyl)-9-hydroxy-7-phenyl-5H-benzo[7]annulen-5-one (3l): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 75.1 mg (93 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.38 (s, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 3H), (m, 1H), (m, 1H), (s, 1H); δ , , , , , , , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 28 H 18 Na 3 [M+Na] + : ; found (furan-2-carbonyl)-9-hydroxy-7-phenyl-5H-benzo[7]annulen-5-one (3m): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 37.0 mg (54 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), 6.61 (s, 1H), (m, 1H), (m, 3H), (m, 3H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); δ , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 22 H 14 Na 4 [M+Na] + : ; found hydroxy-7-phenyl-8-(1-tosyl-1H-pyrrole-2-carbonyl)-5H-benzo[7]annulen-5-on e (3n): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel S8

9 (petroleum ether/ethyl acetate = 10:1), 74.9 mg (76 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.28 (s, 3H), 2.42 (s, 3H), 6.08 (t, J = 4 Hz, 1H), 6.60 (s, 1H), 6.69 (d, J = 4 Hz, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 2H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); δ 20.85, 21.39, , , , , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 30 H 24 N 5 S [M+H] + : ; found (4-chlorobenzoyl)-7-(4-chlorophenyl)-9-hydroxy-5H-benzo[7]annulen-5-one (3o): Yellow solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 64.8 mg (77 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.52 (s, 1H), (m, 2H), (m, 2H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), (m, 1H); (s, 1H); δ , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 24 H 14 Cl 2 Na 3 [M+Na] + : ; found hydroxy-4-(4-methylbenzoyl)-3-phenylcyclohepta-2,4-dien-1-one (3p): White solid, obtained in 1.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 8:1), 43.4 mg (68% yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.15 (s, 3H), 2.89 (brs, 4H), 6.21 (s, 1H), (m, 2H), (m, 5H), (m, 2H), (s, 1H); δ 21.17, 32.70, 41.41, , , , , , , , , , , , , , HRMS (ESI) calcd for C 21 H 18 Na 3 [M+Na] + : ; found S9

10 4. Synthesis of Compounds 5 K 2 C 3 (3.0 equiv) + DMS 110 o C 2h Br 4a 2 5a In a Schlenk tube 1-(2-bromophenyl)-3-(p-tolyl)prop-2-yn-1-one 4a (0.36 mmol, mg), K 2 C 3 (0.9 mmol, mg), DMS (5.0 ml) and 2a (0.30 mmol, 43.8 mg) was stirred at 110 o C under N 2. After the reaction was completed as monitored by thin-layer chromatography, the reaction mixture was then quenched by water, and the water layers were extracted with ethyl acetate (10 ml 3). The combined organic layers were washed with brine, dried over anhydrous Na 2 S 4, filtered, and concentrated under reduced pressure. Purification by chromatography on silica gel (petroleum ether/ethyl acetate = 5:1) afforded desired compound 5a. 7-(p-tolyl)benzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione (5a): Yellow solid, obtained in 2.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 93.5 mg (84 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.34 (s, 3H), 6.77 (s, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 3H), (m, 1H), 8.08 (d, J = 7.6 Hz, 1H), 8.45 (d, J = 8 Hz, 1H); δ , , , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 25 H 16 Na 3 [M+Na] + : ; found S10

11 S11

12 7-phenylbenzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione (5d): Yellow solid, obtained in 2.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 5:1), 81.1 mg (77 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.78 (s, 1H), (m, 6H), (m, 1H), (m, 3H), (m, 1H), 8.80 (d, J = 7.6 Hz, 1H), 8.45 (d, J = 7.6 Hz, 1H); δ ,120.19, , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 24 H 14 Na 3 [M+Na] + : ; found (4-chlorophenyl)benzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione (5e): Yellow solid, obtained in 2.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 5:1), 79.9 mg (69 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.74 (s, 1H), 7.31 (brs, 4H), (m, 1H), (m, 1H), (m, 3H), (m, 1H), 8.09 (d, J = 7.6 Hz, 1H), 8.45 (d, J = 8 Hz, 1H); δ , , , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 24 H 13 ClNa 3 [M+Na] + : ; found (naphthalen-1-yl)benzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione (5f): Yellow solid, obtained in 2.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 5:1), 70.8 mg (59 % yield), mp o C; 1 H NMR (400 MHz, CDCl3) δ 6.90 (s, 1H), (m, 4H), (m, 1H), (m, 8H), 8.04 (d, J = 7.6 Hz, 1H), 8.48 (d, J = 8.0 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 28 H 16 Na 3 [M+Na] + : ; found S12

13 10,11-dimethoxy-7-phenylbenzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione (5g): Yellow solid, obtained in 2.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 5:1), mg (82 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 3.89 (s, 3H), 4.03 (s, 3H), 6.76 (s, 1H), 7.00 (s, 1H), (m, 6H), (m, 2H), (m, 1H), 8.42 (d, J = 8.0 Hz, 1H); δ 56.20,56.46, 99.32, , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 26 H 18 Na 5 [M+Na] + : ; found F 5h 10-fluoro-7-phenylbenzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione (5h): Yellow solid, obtained in 2.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 5:1), 51.1 mg (47 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.79 (s, 1H), 7.36 (brs, 5H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), 7.92 (d, J = 8.0 Hz, 1H), 8.43 (d, J = 8.0 Hz, 1H); δ ( J = 24 Hz ), , ( J = 8.0 Hz ), ( J = 25.5 Hz ), , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 24 H 13 FNa 3 [M+Na] + : ; found fluoro-7-phenylbenzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione (5i): Yellow S13

14 solid, obtained in 2.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 5:1), 85.0 mg (77 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.77 (s, 1H), (m, 1H), (m, 6H), (m, 2H), (m, 1H), (m, 1H), 8.40 (d, J = 7.6 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ ( J = 25.4 Hz ), ( J = 22.7 Hz ), ( J = 12.4 Hz ), , , ( J = 10.9 Hz ), ( J = 10.8 Hz ), , , , , , ( J = 42.5 Hz ), , , , , , , HRMS (ESI) calcd for C 24 H 13 FNa 3 [M+Na] + : ; found chloro-7-phenylbenzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione (5j): Yellow solid, obtained in 2.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 5:1), 46.5 mg (41 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.79 (s, 1H), 7.36 (brs, 5H), (m, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), 8.42 (d, J = 7.6 Hz, 1H); δ , , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 24 H 13 ClNa 3 [M+Na] + : ; found S14

15 C 27 H 19 FNa 6 [M+Na] + : ; found phenylbenzo[3',4']cyclohepta[1',2':5,6]pyrano[2,3-b]pyridine-5,8-dione (5l): Yellow solid, obtained in 2.0 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 2:1), 32.9 mg (31 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.81(s, 1H), 7.37 (brs, 5H), (m, 1H), (m, 2H), (m, 1H), 8.48 (d, J = 7.6 Hz, 1H), 8.61 (d, J = 8 Hz, 1H), 8.77 (d, J = 3.6 Hz, 1H); δ , , , , , , , , , , , , , , , , , , , , HRMS (ESI) calcd for C 23 H 13 NNa 3 [M+Na] + : ; found Gram sacle In a Schlenk tube 1-phenyl-3-(p-tolyl)prop-2-yn-1-one 1a (10 mmol, 2.20 g), Cs 2 C 3 (30 mmol, 9.77 g), DMS(50 ml) and 1H-indene-1,3(2H)-dione 2a (14 mmol, 2.04 g) was stirred at 110 o C under N 2. After the reaction was completed as monitored by thin-layer chromatography, the reaction mixture was then quenched by water, and the water layers were extracted with ethyl acetate (30 ml 3). The combined organic layers were washed with brine, dried over anhydrous Na 2 S 4, filtered, and concentrated under reduced pressure. Purification by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1) afforded desired compound 3a (2.82 g). S15

16 In a Schlenk tube 1-(2-bromophenyl)-3-phenylprop-2-yn-1-one 4d (4.8 mmol, 1.37 g), K 2 C 3 (12 mmol, 1.66 g), DMS (67 ml) and 2a (4 mmol, 0.58 g) was stirred at 110 o C under N 2. After the reaction was completed as monitored by thin-layer chromatography, the reaction mixture was then quenched by water, and the water layers were extracted with ethyl acetate (20 ml 3). The combined organic layers were washed with brine, dried over anhydrous Na 2 S 4, filtered, and concentrated under reduced pressure. Purification by chromatography on silica gel (petroleum ether/ethyl acetate = 5:1) afforded desired compound 5d (0.995 g). 6. Synthesis of Compound 6a In a Schlenk tube 1-(2-bromophenyl)-3-(p-tolyl)prop-2-yn-1-one 4a (0.36 mmol, mg), K 2 C 3 (0.9 mmol, mg), DMS (5.0 ml) and 2a (0.30 mmol, 43.8 mg) was stirred at room temperature under N 2. After the reaction was completed as monitored by thin-layer chromatography, the reaction mixture was then quenched by water, and the water layers were extracted with ethyl acetate (10 ml 3). The combined organic layers were washed with brine, dried over anhydrous Na 2 S 4, S16

17 filtered, and concentrated under reduced pressure. Purification by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1) afforded desired compound 6a. 8-(2-bromobenzoyl)-9-hydroxy-7-(p-tolyl)-5H-benzo[7]annulen-5-one (6a). Yellow solid, obtained in 12 h and purified by chromatography on silica gel (petroleum ether/ethyl acetate = 10:1), 69.5 mg (52 % yield), mp o C; 1 H NMR (400 MHz, CDCl 3, TMS): δ 2.23 (s, 3H), 6.47 (s, 1H), (m, 5H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), (s, 1H); 13 C NMR (100 MHz, CDCl 3, TMS): δ 20.75, , , , , , , , , , , , , , , , , , , , , , ; HRMS (ESI) for C 25 H 17 BrNa 3 [M+Na] + : calcd , found S17

18 7. Copies of Spectra of New Products 1 H NMR (400 MHz, CDCl 3 ) S18

19 Me H 3b Ph Me H 3b Ph S19

20 S20

21 S21

22 S22

23 S23

24 S24

25 S25

26 S26

27 S27

28 S28

29 S29

30 S30

31 S31

32 S32

33 S33

34 S34

35 Me 5b Me 5b S35

36 S36

37 S37

38 S38

39 5f 5f S39

40 S40

41 S41

42 F 5i F 5i S42

43 S43

44 S44

45 S45

46 S46

47 8. X-ray Crystallography of Compound 5a 7-(p-tolyl)benzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione(5a, CCDC ) (rtep ellipsoids are depicted at the 50% level) Table 1. Crystal data and structure refinement for 5a Identification code Empirical formula 5a C25 H16 3 Formula weight Temperature Wavelength 293(2) K Å Crystal system, space group Triclinic, P -1 Unit cell dimensions a = (16) Å α=92.612(4). Volume 895.1(3) Å 3 Z, Calculated density 2, Mg/m 3 Absorption coefficient mm -1 F(000) 380 b = (17) Å β= (4). c = (2) Å γ = (4). Crystal size x x mm 3 Theta range for data collection to Limiting indices -10<=h<=9, -10<=k<=11, -7<=l<=14 Reflections collected / unique 5374/3519 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3519 / 0 / 254 Goodness-of-fit on F^ Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S47

48 S48

49 9. X-ray Crystallography of Compound 6a 8-(2-bromobenzoyl)-9-hydroxy-7-(p-tolyl)-5H-benzo[7]annulen-5-one (6a, CCDC ) (rtep ellipsoids are depicted at the 50% level) Table 1. Crystal data and structure refinement for 6a Identification code Empirical formula Formula weight Temperature Wavelength 6a C25 H17 Br 3 293(2) K Å Crystal system, space group Monoclinic, P 21/c Unit cell dimensions a = (4) Å α= 90 b = (4) Å β= (6) Volume (12) Å 3 c = (6) Å γ = 90. Z, Calculated density 4, Mg/m 3 Absorption coefficient mm -1 F(000) 904 Crystal size x x mm 3 Theta range for data collection to Limiting indices -12<=h<=12, -14<=k<=13, -15<=l<=19 Reflections collected / unique 10132/3665 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3665 / 0 / 264 Goodness-of-fit on F^ Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S49

50 S50