Supporting Information

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 200241, China. Fax: (+86) 021-54340096, E-mail: yzli@chem.ecnu.edu.cn Table of Contents 1. General Details.... 2 2. Preparation of Acetyenic Ketones... 2 3. Synthesis of Compounds 3... 3 4. Synthesis of Compounds 5... 10 5. Gram sacle... 15 6. Synthesis of Compound 6a... 16 7. Copies of Spectra of New Products... 18 8. X-ray Crystallography of Compound 5a... 47 9. X-ray Crystallography of Compound 6a... 49 S1

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 = 77.00 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

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, 195.5 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

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 83.7-85.8 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.17 (s, 3H), 6.55 (s, 1H), 6.81-6.84 (m, 2H), 6.90-6.93 (m, 2H), 7.10-7.15 (m, 2H), 7.24-7.32 (m, 3H), 7.78-7.82 (m, 2H), 8.03-8.05 (m, 1H), 8.55-8.57 (m, 1H), 15.47 (s, 1H); δ 20.72, 114.01, 127.94, 127.98, 128.02, 128.40, 128.97, 129.15, 130.28, 131.62, 131.66, 132.16, 133.41, 138.54, 140.20, 140.40, 142.60, 147.18, 171.49, 192.93, 202.50. HRMS (ESI) calcd for C 25 H 18 Na 3 [M+Na] + : 389.1148; found 389.1153. 8-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 72.8-74.8 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 3.67 (s, 3H), 6.52-6.54 (m, 2H), 6.56 (s, 1H), 6.93-6.96 (m, 2H), 7.11-7,16 (m, 2H), 7.22-7.26 (m, 1H), 7.30-7.33 (m, 2H), 7.76-7.80 (m, 2H), 8.02-8.06 (m, 1H), 8.53-8.56 (m, 1H), 15.41 (s, 1H); δ 55.11, 113.88, 127.86, 127.98, 128.05, 128.96, 129.39, 130.25, 131.57, 131.69, 132.10, 133.39, 135.60, 140.41, 142.64, 146.84, 160.02, 171.39, 192.83, 202.45. HRMS (ESI) calcd for C 25 H 18 Na 4 [M+Na] + : 405.1097; found 405.1107. 8-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 80.0-82.1 o C; 1 H NMR (400 MHz, CDCl 3 ) δ S4

6.56 (s, 1H), 7.02 (brs, 4H), 7.10-7,15 (m, 2H), 7.23-7.31 (m, 4H), 7.79-7.82 (m, 2H), 8.02-8.06 (m, 1H), 8.55-8.59 (m, 1H), 15.56 (s, 1H); δ 113.85, 128.00, 128.04, 128.06, 128.39, 128.44, 128.84, 128.96, 130.30, 131.61, 131.68, 132.23, 133.47, 140.36, 142.54, 143.01, 147.06, 171.82, 192.92, 202.42. HRMS (ESI) calcd for C 24 H 16 Na 3 [M+Na] + : 375.0992; found 375.0996. 8-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 83.5-85.5 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.50 (s, 1H), 6.93-7.01 (m, 4H), 7.14-7,19 (m, 2H), 7.28-7,31 (m, 3H), 7.79-7.82 (m, 2H), 8.00-8.04 (m, 1H), 8.54-8.57 (m, 1H), 15.63 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 113.42, 128.04, 128.21, 128.59, 128.89, 128.97, 129.18, 130.37, 131.55, 131.93, 132.34, 133.61, 134.43, 140.22, 141.50, 142.47, 145.78, 172.34, 192.74, 202.12. HRMS (ESI) calcd for C 24 H 16 Cl 3 [M+H] + : 387.0782; found 387.0789. 8-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 147.2-149.3 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.69 (s, 3H), 4.82 (s, 2H), 7.48-7.52 (m, 2H), 7.58-7.61 (m, 1H), 7.73-7.77 (m, 2H), 7.84-7.88 (m, 1H), 7.93-7.95 (m, 1H), 8.03 (d, J = 8.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 22.81. 45.72, 123.23, 123.26, 128.46, 128.97, 133.72, 135.20, 135.37, 135.82, 137.02, 141.02, 141.59, 164.92, 191.19, 191.40, 195.97. HRMS (ESI) calcd for C 19 H 14 Na 3 [M+H] + : 313.0835; found 313.0835. S5

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 129.7-131.1 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), 7.02-7.10 (m, 5H), 7.80-7.83 (m, 2H), 8.02-8.05 (m, 1H), 8.55-8.58 (m, 1H), 15.19 (s, 1H); δ 56.07, 60.70, 105.74, 113.98, 128.00, 128.34, 128.46, 128.97, 130.28, 131.46, 132.23, 133.51, 135.59, 141.14, 142.63, 142.97, 147.24, 152.85, 171.14, 192.80, 201.75 HRMS (ESI) calcd for C 27 H 22 Na 6 [M+Na] + : 465.1309; found 465.1300. 9-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 117.2-119.3 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 3.76 (s, 3H), 6.58 (s, 1H), 6.62-6.65 (m, 2H), 7.04-7.12 (m, 5H), 7.37-7.40 (m, 2H), 7.78-7.81 (m, 2H), 8.03-8.06 (m, 1H), 8.55-8.58 (m, 1H), 15.39 (s, 1H); δ 55.23, 113.35, 127.88, 128.45, 128.51, 128.94, 130.29, 130.74, 131.75, 132.20, 132.80, 133.28, 142.40, 143.03, 147.32, 162.86, 170.90, 192.97, 200.75. HRMS (ESI) calcd for C 25 H 18 Na 4 [M+Na] + : 405.1097; found 405.1103. 9-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 121.9-124.3 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.26 (s, 3H), 6.57 (s, 1H), 6.91-6.94 (m, 2H), 7.04 (brs, 4H), 7.22-7,27 (m, 3H), 7.78-7.82 (m, 2H), 8.03-8.06 (m, 1H), 8.55-8.59 (m, 1H), 15.51 (s, 1H); δ 21.22, 113.86, 128.01, 128.36, 128.39, 128.71, 128.74, 128.98, 130.31, 131.73, 132.22, 133.37, 137.61, 142.49, 142.59, 143.07, 147.28, 171.39, 192.97, 202.08. HRMS (ESI) calcd for C 25 H 19 3 [M+H] + : 367.1329; found 367.1335. S6

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 135.1-137.0 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.50 (s, 1H), 6.71-6.76 (m, 2H), 6.97-6.99 (m, 5H), 7.25-7,28 (m, 2H), 7.72-7.75 (m, 2H), 7.94-7.97 (m, 1H), 8.47-8.50 (m, 1H), 15.38 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 113.60, 115.21 (J = 21.8 Hz), 127.93, 128.61, 128.92 (J = 10.3 Hz), 130.35, 130.67 (J = 9.2 Hz), 131.52, 132.30, 133.59, 136.54, 142.71 (J = 36.4 Hz), 146.78, 163.57, 166.10, 171.91, 192.96, 200.82. HRMS (ESI) calcd for C 24 H 16 F 3 [M+H] + : 371.1078; found 371.1081. 8-(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 94.7-96.3 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.57 (s, 1H), 7.03-7,12 (m, 7H), 7.23-7.26 (m, 2H), 7.79-7.83 (m, 2H), 8.01-8.05 (m, 1H), 8.54-8.57 (m, 1H), 15.48 (s, 1H); δ 113.63, 128.01, 128.36, 128.62, 128.68, 128.98, 129.45, 130.35, 131.47, 132.29, 133.64, 137.99, 138.66, 142.59, 142.85, 146.57, 172.16, 192.86, 200.99. HRMS (ESI) calcd for C 24 H 16 Cl 3 [M+H] + : 387.0782; found 387.0786. 8-(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 135.7-137.7 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.56 (s, 1H), 7.02-7,08 (m, 4H), 7.14-7.17 (m, 2H), 7.24-7.27 (m, 3H), 7.79-7.83 (m, 2H), 8.01-8.04 (m, 1H), 8.54-8.57 (m, 1H), 15.47 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 113.63, 126.46, 128.02, 128.60, 128.69, 128.98, 129.53, 130.34, S7

131.32, 131.45, 132.29, 133.64, 139.08, 142.55, 142.83, 146.58, 172.19, 192.85, 201.11. HRMS (ESI) calcd for C 24 H 15 BrNa 3 [M+Na] + : 453.0097; found 453.0114. 8-(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 163.9-165.9 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.38 (s, 1H), 6.60-6.62 (m, 1H), 6.67-6.72 (m, 2H), 6.75-6.78 (m, 2H), 7.24-7.26 (m, 1H), 7.30-7.32 (m, 1H), 7.35-7.38 (m, 2H), 7.62-7.65 (m, 1H), 7.68-7.71 (m, 1H), 7.80-7.86 (m, 3H), 8.00-8.02 (m, 1H), 8.58-8.61 (m, 1H), 16.40 (s, 1H); δ 115.68, 124.28, 125.58, 126.31, 126.76, 126.97, 127.25, 127.37, 128.02, 128.08, 128.88, 129.20, 129.26, 130.29, 131.69, 131.82, 132.21, 133.42, 133.58, 137.77, 142.74, 142.79, 147.31, 173.84, 192.91, 203.05. HRMS (ESI) calcd for C 28 H 18 Na 3 [M+Na] + : 425.1148; found 425.1157. 8-(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 78.8-80.1 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.18-6.19 (m, 1H), 6.61 (s, 1H), 6.88-6.90 (m, 1H), 7.07-7.11 (m, 3H), 7.26-7.31 (m, 3H), 7.69-7.72 (m, 2H), 7.92-7.94 (m, 1H), 8.43-8.46 (m, 1H), 14.99 (s, 1H); δ 112.52, 119.82, 127.02, 127.58, 128.59, 128.79, 128.82, 129.19, 130.28, 131.48, 132.14, 133.39, 142.60, 145.61, 146.52, 151.89, 170.99, 186.70, 193.05. HRMS (ESI) calcd for C 22 H 14 Na 4 [M+Na] + : 365.0784; found 365.0791. 9-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

(petroleum ether/ethyl acetate = 10:1), 74.9 mg (76 % yield), mp 168.2-170.2 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), 7.03-7.06 (m, 2H), 7.13-7.16 (m, 2H), 7.25-7.27 (m, 1H), 7.30-7.33 (m, 2H), 7.75-7.78 (m, 2H), 7.86-7.89 (m, 2H), 7.95-7.99 (m, 1H), 8.45-8.48 (m, 1H), 15.41 (s, 1H); δ 20.85, 21.39, 110.92, 113.56, 122.94, 128.04, 128.21, 128.32, 128.44, 128.54, 129.58, 129.71, 130.17, 131.57, 132.04, 133.38, 136.63, 138.69, 139.38, 142.81, 145.18, 146.94, 172.15, 188.93, 193.25. HRMS (ESI) calcd for C 30 H 24 N 5 S [M+H] + : 510.1370; found 510.1380. 8-(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 88.1-89.9 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.52 (s, 1H), 6.96-6.99 (m, 2H), 7.05-7.08 (m, 2H), 7.15-7.18 (m, 2H), 7.26-7.29 (m, 1H), 7.80-7.85 (m, 2H), 8.00-8.03 (m, 1H), 8.53-8.57 (m, 1H); 15.51 (s, 1H); δ 113.16, 128.56, 128.82, 128.99, 129.08, 129.17, 129.50, 130.43, 131.41, 132.42, 133.80, 134.82, 138.38, 138.51, 141.33, 142.59, 145.24, 172.58, 192.70, 200.64. HRMS (ESI) calcd for C 24 H 14 Cl 2 Na 3 [M+Na] + : 443.0212; found 443.0220. 5-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 181.6-182.9 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.15 (s, 3H), 2.89 (brs, 4H), 6.21 (s, 1H), 6.80-6.83 (m, 2H), 6.94-7.01 (m, 5H), 7.14-7.20 (m, 2H), 16.78 (s, 1H); δ 21.17, 32.70, 41.41, 110.86, 127.09, 127.74, 128.21, 128.67, 128.69, 128.84, 134.50, 142.48, 143.23, 151.21, 192.78, 195.68, 202.74. HRMS (ESI) calcd for C 21 H 18 Na 3 [M+Na] + : 341.1148; found 341.1158. S9

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, 107.7 mg), K 2 C 3 (0.9 mmol, 124.2 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 124.4-126.9 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 2.34 (s, 3H), 6.77 (s, 1H), 7.13-7.16 (m, 2H), 7.26-7.28 (m, 2H), 7.36-7.41 (m, 1H), 7.57-7.60 (m, 1H), 7.70-7.84 (m, 3H), 7.89-7.92 (m, 1H), 8.08 (d, J = 7.6 Hz, 1H), 8.45 (d, J = 8 Hz, 1H); δ 21.00. 117.79, 120.19, 123.30, 125.65, 126.41, 126.63, 128.43, 128.54, 129.40, 129.90, 131.80, 132.72, 133.26, 134.48, 138.40, 139.00, 143.50, 144.42, 155.53, 160.80, 176.98, 192.69. HRMS (ESI) calcd for C 25 H 16 Na 3 [M+Na] + : 387.0992; found 387.0996. S10

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 228.4-230.5 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.78 (s, 1H), 7.34-7.42 (m, 6H), 7.59-7.62 (m, 1H), 7.74-7.86 (m, 3H), 7.90-7.93 (m, 1H), 8.80 (d, J = 7.6 Hz, 1H), 8.45 (d, J = 7.6 Hz, 1H); δ 117.82,120.19, 123.33, 125.72, 126.53, 126.67, 128.49, 128.59, 128.62, 129.95, 131.90, 132.80, 133.79, 134.55, 141.93, 143.50, 144.47, 155.59, 160.90, 176.92, 192.68. HRMS (ESI) calcd for C 24 H 14 Na 3 [M+Na] + : 373.0835; found 373.0840. 7-(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 230.7-232.1 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.74 (s, 1H), 7.31 (brs, 4H), 7.40-7.44 (m, 1H), 7.60-7.63 (m, 1H), 7.74-7.88 (m, 3H), 7.90-7.93 (m, 1H), 8.09 (d, J = 7.6 Hz, 1H), 8.45 (d, J = 8 Hz, 1H); δ 117.88, 119.80, 123.22, 125.90, 126.63, 127.87, 128.55, 128.65, 128.90, 129.89, 132.03, 132.96, 133.89, 134.39, 134.73, 140.48, 143.27, 143.46, 155.61, 161.16, 176.87, 192.43. HRMS (ESI) calcd for C 24 H 13 ClNa 3 [M+Na] + : 407.0445; found 407.0453. 7-(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 218.3-231.8 o C; 1 H NMR (400 MHz, CDCl3) δ 6.90 (s, 1H), 7.36-7.48 (m, 4H), 7.60-7.63 (m, 1H), 7.72-7.95 (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 117.82, 120.19, 123.33, 125.72, 126.53, 126.67, 128.49, 128.59, 128.62, 129.95, 131.90, 132.80, 133.79, 134.55, 141.93, 143.50, 144.47, 155.59, 160.90, 176.92, 192.68. HRMS (ESI) calcd for C 28 H 16 Na 3 [M+Na] + : 423.0992; found 423.0996. S12

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), 100.7 mg (82 % yield), mp 259.6-260.8 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), 7.34-7.42 (m, 6H), 7.74-7.84 (m, 2H), 7.90-7.93 (m, 1H), 8.42 (d, J = 8.0 Hz, 1H); δ 56.20,56.46, 99.32, 105.12, 116.67, 119.62, 126.47, 128.37, 128.47, 128.53, 130.09, 131.78, 132.49, 133.64, 142.24, 143.31, 144.81, 148.24, 151.65, 155.34, 160.40, 175.78, 192.71. HRMS (ESI) calcd for C 26 H 18 Na 5 [M+Na] + : 433.1046; found 433.1047. 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 129.7-134.2 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.79 (s, 1H), 7.36 (brs, 5H), 7.44-7.50 (m, 1H), 7.61-7.65 (m, 1H), 7.71-7.74 (m, 1H), 7.78-7.87 (m, 2H), 7.92 (d, J = 8.0 Hz, 1H), 8.43 (d, J = 8.0 Hz, 1H); δ 111.52 ( J = 24 Hz ), 119.52, 120.06 ( J = 8.0 Hz ), 120.81 ( J = 25.5 Hz ), 123.57, 124.39, 126.52, 128.57, 128.70, 129.73, 131.96, 132.99, 134.01, 141.71, 143.61, 144.15, 151.82, 161.14, 176.24, 192.60. HRMS (ESI) calcd for C 24 H 13 FNa 3 [M+Na] + : 391.0741; found 391.0745. 11-fluoro-7-phenylbenzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione (5i): Yellow S13

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 251.9-253.6 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.77 (s, 1H), 7.10-7.15 (m, 1H), 7.25-7.36 (m, 6H), 7.78-7.84 (m, 2H), 7.89-7.92 (m, 1H), 8.07-8.11 (m, 1H), 8.40 (d, J = 7.6 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 104.50 ( J = 25.4 Hz ), 114.50 ( J = 22.7 Hz ), 120.18 ( J = 12.4 Hz ), 126.48, 128.44, 128.58 ( J = 10.9 Hz ), 129.33 ( J = 10.8 Hz ), 129.55, 131.93, 132.96, 133.96, 141.75, 143.80 ( J = 42.5 Hz ), 156.46, 156.59, 161.13, 165.12, 167.68, 175.93, 192.49. HRMS (ESI) calcd for C 24 H 13 FNa 3 [M+Na] + : 391.0741; found 391.0747. 10-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 236.7-238.1 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.79 (s, 1H), 7.36 (brs, 5H), 7.56-7.59 (m, 1H), 7.66-7.70 (m, 1H), 7.78-7.87 (m, 2H), 7.90-7.93 (m, 1H), 8.03-8.05 (m, 1H), 8.42 (d, J = 7.6 Hz, 1H); δ 119.64, 120.18, 124.21, 126.08, 126.54, 128.56, 128.60, 128.70, 129.63, 131.74, 131.96, 133.05, 134.01, 134.80, 141.63, 143.61, 144.06, 153.92, 161.09, 175.87, 192.53. HRMS (ESI) calcd for C 24 H 13 ClNa 3 [M+Na] + : 407.0445; found 407.0452. S14

C 27 H 19 FNa 6 [M+Na] + : 481.1058; found 481.1058. 7-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 250.3-252.6 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.81(s, 1H), 7.37 (brs, 5H), 7.46-7.50 (m, 1H), 7.80-7.89 (m, 2H), 7.92-7.95 (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 118.04, 120.50, 122.74, 126.60, 128.52, 128.65, 128.70, 129.18, 129.39, 132.15, 133.28, 134.25, 137.42, 141.51, 143.57, 143.68, 154.23, 160.00, 161.42, 177.53, 192.44. HRMS (ESI) calcd for C 23 H 13 NNa 3 [M+Na] + : 374.0788; found 374.0788. 5. 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

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, 107.7 mg), K 2 C 3 (0.9 mmol, 124.2 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

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 157.1-159.8 o C; 1 H NMR (400 MHz, CDCl 3, TMS): δ 2.23 (s, 3H), 6.47 (s, 1H), 6.8-6.96(m, 5H), 7.01-7.05 (m, 2H), 7.26-7.29 (m, 1H), 7.78-7.82 (m, 2H), 7.96-7.99 (m, 1H), 8.51-8.54 (m, 1H), 16.02 (s, 1H); 13 C NMR (100 MHz, CDCl 3, TMS): δ 20.75, 115.10, 119.75, 126.73, 127.16, 128.76, 129.36, 129.43, 129.93, 130.28, 131.19, 131.66, 132.13, 133.36, 133.63, 138.41, 140.34, 140.87, 142.90, 146.01, 174.03, 192.95, 200.91; HRMS (ESI) for C 25 H 17 BrNa 3 [M+Na] + : calcd 467.0260, found 467.0253. S17

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

Me H 3b Ph Me H 3b Ph S19

Me 5b Me 5b S35

5f 5f S39

F 5i F 5i S42

8. X-ray Crystallography of Compound 5a 7-(p-tolyl)benzo[6,7]cyclohepta[1,2-b]chromene-5,8-dione(5a, CCDC-1815273) (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 364.38 Temperature Wavelength 293(2) K 0.71073 Å Crystal system, space group Triclinic, P -1 Unit cell dimensions a = 8.3697(16) Å α=92.612(4). Volume 895.1(3) Å 3 Z, Calculated density 2, 1.352 Mg/m 3 Absorption coefficient 0.088 mm -1 F(000) 380 b = 9.3019(17) Å β= 100.852(4). c = 11.724(2) Å γ = 91.184(4). Crystal size 0.200 x 0.170 x 0.120 mm 3 Theta range for data collection 2.193 to 26.000. Limiting indices -10<=h<=9, -10<=k<=11, -7<=l<=14 Reflections collected / unique 5374/3519 [R(int) = 0.0239] Completeness to theta = 25.242 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7456 and 0.6520 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3519 / 0 / 254 Goodness-of-fit on F^2 1.044 Final R indices [I>2sigma(I)] R1 = 0.0490, wr2 = 0.1260 R indices (all data) R1 = 0.0702, wr2 = 0.1420 Largest diff. peak and hole 0.168 and -0.215 e.å -3 S47

9. X-ray Crystallography of Compound 6a 8-(2-bromobenzoyl)-9-hydroxy-7-(p-tolyl)-5H-benzo[7]annulen-5-one (6a, CCDC-1815272) (rtep ellipsoids are depicted at the 50% level) Table 1. Crystal data and structure refinement for 6a Identification code Empirical formula Formula weight 445.29 Temperature Wavelength 6a C25 H17 Br 3 293(2) K 0.71073 Å Crystal system, space group Monoclinic, P 21/c Unit cell dimensions a = 10.733(4) Å α= 90 b = 11.633 (4) Å β= 100.221(6) Volume 1974.8(12) Å 3 c = 16.071(6) Å γ = 90. Z, Calculated density 4, 1.498 Mg/m 3 Absorption coefficient 2.106 mm -1 F(000) 904 Crystal size 0.190 x 0.160 x 0.100 mm 3 Theta range for data collection 1.928 to 25.500.. Limiting indices -12<=h<=12, -14<=k<=13, -15<=l<=19 Reflections collected / unique 10132/3665 [R(int) = 0.0878] Completeness to theta = 25.242 99.9 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7456 and 0.5487 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3665 / 0 / 264 Goodness-of-fit on F^2 0.978 Final R indices [I>2sigma(I)] R1 = 0.0563, wr2 = 0.1347 R indices (all data) R1 = 0.1154, wr2 = 0.1637 Largest diff. peak and hole 1.125 and -0.605 e.å -3 S49