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1 Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 Supplementary Information Oxidative Tandem Annulation of 1 (2 Ethynylaryl)prop 2 en 1 ones Catalyzed by Cooperative Iodine and TBHP Bang Liu, Jiang Cheng, Yang Li,* and Jin-Heng Li* Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University, Nanchang , China, and School of Petrochemical Engineering, Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, Changzhou University, Changzhou , China liyang @126.com and jhli@hnu.edu.cn List of Contents (A) Typical experimental procedures (B) Analytical data (C) References (D) Spectra (E) The X-ray single-crystal diffraction analysis

2 (A) Typical experimental procedures (a) General The 1 H and 13 C NMR spectra were recorded in CDCl3 solvent on a NMR spectrometer using TMS as internal standard. HRMS was measured on an electrospray ionization (ESI) apparatus using time-of-flight (TOF) mass spectrometry. Melting points are uncorrected. The instrument for electrolysis is DC power source (PM3005B) (made in China). Cyclic voltammograms were obtained on a CHI 605E potentiostat. The anode electrode is graphite rod (Φ6mm 80mm) and cathode electrode is platinum electrodes ( cm 2 ). Starting materials (1-(2-ethynylaryl)prop-2-en-1-ones) 1 were synthesized according to the literature procedures (b) General procedure for the oxidative tandem annulation of 1-(2- ethynylaryl)prop-2-en-1-ones (1): To a 25 ml Schlenk tube were added I2 (40 mol %), 1,6-enyne 1a (0.2 mmol), and 1,4-dioxane/H2O (v/v=10/1; 3.3 ml). Then TBHP (70%w in water) 4 equiv. was added to the solution. The mixture was stirred at 80 o C under argon atmosphere for 14 h until complete consumption of starting material as monitored by TLC and/or GC-MS analysis. After the reaction was finished, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and washed with Na2S2O3 and saturated NaCl. The aqueous phase was extracted twice with ethyl acetate and washed with saturated

3 NaCl. The combined organic phases were dried over anhydrous Na2SO4 and concentrated, then purified by column chromatography (petroleum ether/ethyl acetate, v/v=15/1) to afford 2a (86% yield, 55.7 mg). 1 mmol scale To a 25 ml Schlenk tube were added I2 (40 mol %), 1,6-enyne 1a (1 mmol), and 1,4-dioxane/H2O (v/v=10/1; 5.5 ml). Then TBHP (70% solution in water) 4 equiv. was added to the solution. The mixture was stirred at 80 o C under argon atmosphere for 14 h until complete consumption of starting material as monitored by TLC and/or GC-MS analysis. After the reaction was finished, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and washed with Na2S2O3 and saturated NaCl. The aqueous phase was extracted twice with ethyl acetate and washed with saturated NaCl. The combined organic phases were dried over anhydrous Na2SO4 and concentrated, then purified by column chromatography (petroleum ether/ethyl acetate, v/v=15/1) to afford 2a (90% yield, 290 mg). (B) Analytical data 1,1a-Diphenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2a) 5 86% yield, 55.7mg; 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 3H), (m, 5H), 6.76 (d, J = 7.2 Hz, 2H), 3.67 (d, J = 5.6 Hz, 1H), 3.42 (d, J = 5.6 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 192.7, 191.0, 134.4, 134.2, 133.3, 132.5, 132.5, 131.8, 131.6, 128.1, 128.0, 128.0, 127.5, 126.8, 50.9, 43.0, 39.9; LRMS (EI, 70 ev) m/z (%): 324 (M +, 100), 279 (35), 265 (29).

4 % [MS Spectrum] # of Peaks 355 Raw Spectrum (scan: 3539) Base Peak m/z (Inten: 600,271) Background No Background Spectrum m/z Absolute Intensity Relative Intensity

5 (x1,000,000) TIC

6 % [MS Spectrum]# of Peaks 301 Raw Spectrum (scan : 3146) Base Peak m/z (Inten : 395,810) Background (scan : 3190) m/z Absolute Intensity Relative Intensity

7 (x10,000,000) TIC % [MS Spectrum] # of Peaks 287 Raw Spectrum (scan : 3147) Base Peak m/z (Inten : 223,890) Background (scan : 3191) m/z Absolute Intensity Relative Intensity

8 Phenyl-1a-(p-tolyl)-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2b) 83% yield, 56.1 mg; 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 3H), (m, 4H), 6.77 (d, J = 7.2 Hz, 2H), 3.63 (d, J = 5.2 Hz, 1H), 3.40 (d, J = 5.2 Hz, 1H), 2.28 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 192.8, 191.3, 137.7, 134.4, 134.1, 133.5, 132.5, 131.6, 128.8, 128.5, 128.0, 128.0, 127.4, 126.7, 50.6, 43.1, 40.1, 21.2; LRMS (EI, 70 ev) m/z (%): 338 (M +, 100), 323 (25), 279 (20); HRMS (ESI): calcd for C24H19O2 [M+H + ] , found

9 1a-(4-Chlorophenyl)-1-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7- dione (2c) 73% yield, 52.2 mg; 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), 7.21 (d, J = 7.2 Hz, 2H ), (m, 5H), 6.77 (d, J = 6.8 Hz, 2H), 3.64 (d, J = 4.8 Hz, 1H), 3.43 (d, J = 4.8 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 192.3, 190.7, 134.5, 134.3, 134.0, 133.1, 132.9, 132.4, 132.2, 130.2, 128.3, 128.2, 128.0, 127.9, 127.7, 126.8, 50.0, 42.9, 39.5; LRMS (EI, 70 ev) m/z (%): 360 (M + +2, 36), 358 (M +, 100), 323 (37); HRMS (ESI): calcd for C23H16 35 ClO2 [M+H + ] , found Methyl 4-(2,7-dioxo-1-phenyl-1,2,7,7a-tetrahydro-1aH-cyclopropa[b]naphthalen- 1a-yl)-3-methylbenzoate (2d) 81% yield; 64.1 mg 1 H NMR (400 MHz, CDCl3) δ (m, 2.8H), 7.91 (d, J = 8.8 Hz, 1.4H), (m, 2.8H), 7.69 (s, 0.8H), (m, 1.4H), (m, 2.4H), 7.04 (t, J = 7.2 Hz, 2H), 6.82 (d, J = 7.6 Hz, 0.8H), 6.65 (d, J = 8.0 Hz, 2H), 6.57 (d, J = 8.0 Hz, 0.4H), 3.89 (s, 3H), 3.86 (s, 1.2H), 3.58 (d, J = 5.6 Hz, 1H), 3.53 (d, J = 5.6 Hz, 0.4H), 3.48 (d, J = 5.6 Hz, 1H), 3.39 (d, J = 5.6 Hz, 0.4H), 2.37 (s, 1.2H), 1.85 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ 192.3, 191.2, 190.0, 166.8, 141.1, 138.7, 136.2, 135.6, 134.5, 134.4, 134.2, 133.5, 133.4, 133.3, 132.5, 132.4, 132.3, 132.2, 131.8, 131.5, 131.1, 130.0, 129.7, 128.3, 128.2, 127.9, 127.9, 127.9, 127.7, 127.4, 127.0, 126.8, 126.6, 126.0, 52.1, 52.0, 50.5, 48.6, 43.5, 43.1, 41.8, 41.1, 20.0, 19.6; LRMS (EI, 70 ev) m/z (%): 396 (M +, 100), 337 (23), 293 (14); HRMS (ESI): calcd for C26H21O4 [M+H + ] , found

10 1a-Cyclopropyl-1-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2e) 50% yield, 28.8 mg; 1 H NMR (400 MHz, CDCl3) δ 8.17 (d, J = 7.2 Hz, 1H), 8.02 (d, J = 6.8 Hz, 1H), (m, 2H), (m, 5H), 3.24 (d, J = 5.6 Hz, 1H), 2.97 (d, J = 5.6 Hz, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 1H); 13 C NMR (100 MHz, CDCl3) δ 194.2, 193.4, 134.2, 134.0, 133.7, 132.5, 132.1, 128.9, 128.3, 127.5, 127.5, 126.6, 45.4, 42.7, 36.5, 8.6, 4.4; LRMS (EI, 70 ev) m/z (%): 288 (M +, 52), 273 (23), 91 (100); HRMS (ESI): calcd for C20H17O2 [M+H + ] , found a-Butyl-1-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2f) 80% yield; 48.6 mg 1 H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 6.8 Hz, 1H), 8.03 (d, J = 7.2 Hz, 1H), (m, 2H), (m, 3H), 7.22 (d, J = 7.2 Hz, 2H), 3.25 (d, J = 5.6 Hz, 1H), 3.06 (d, J = 5.6 Hz, 1H), (m, 1H), (m, 4H), 0.81 (t, J = 7.2 Hz, 3H), (m, 1H); 13 C NMR (100 MHz, CDCl3) δ 193.8, 193.8, 134.1, 134.0, 133.6, 132.6, 132.5, 128.8, 128.5, 127.7, 127.4, 126.6, 44.6, 42.7, 38.3, 29.3, 27.0, 22.7, 13.9; LRMS (EI, 70 ev) m/z (%): 304 (M +, 100), 247 (47), 203 (62); HRMS (ESI): calcd for C21H21O2 [M+H + ] , found (2,7-Dioxo-1-phenyl-1,2,7,7a-tetrahydro-1aH-cyclopropa[b]naphthalen-1ayl)ethyl benzoate (2g) 73% yield, 57.8 mg; 1 H NMR (400 MHz, CDCl3) δ 8.16 (d, J = 7.2 Hz, 1H), 8.04 (d, J = 6.8 Hz, 1H), 7.91 (d, J = 7.6 Hz, 2H), (m, 2H), 7.52 (t, J = 7.2 Hz, 1H), (m, 5H), 7.24 (d, J = 7.6 Hz, 2H), (m, 1H), (m, 1H), 3.28 (d, J = 5.6 Hz, 1H), 3.22 (d, J = 5.6 Hz, 1H),

11 (m, 1H), (m, 1H); 13 C NMR (100 MHz, CDCl3) δ 193.1, 192.8, 166.4, 134.2, 134.1, 133.0, 132.9, 132.4, 132.3, 129.8, 129.5, 128.8, 128.7, 128.3, 128.0, 127.4, 126.7, 62.2, 41.3, 41.3, 38.0, 26.9; LRMS (EI, 70 ev) m/z (%): 396 (M +, 3), 274 (100), 229 (16); HRMS (ESI): calculated for C26H21O4 [M+H + ] , found a-Phenyl-1-(p-tolyl)-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2h) 5 89% yield, 60.1 mg; 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 5H), 6.88 (d, J = 7.6 Hz, 2H), 6.62 (d, J = 7.6 Hz, 2H), 3.63 (d, J = 5.2 Hz, 1H), 3.39 (d, J = 5.2 Hz, 1H), 2.21 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 192.8, 191.1, 137.3, 134.4, 134.1, 132.5, 131.8, 131.7, 130.3, 128.7, 128.0, 128.0, 127.9, 127.8, 126.7, 50.9, 43.0, 40.1, 21.0; LRMS (EI, 70 ev) m/z (%): 338 (M +, 100), 279 (53), 293 (23). 1-(4-(Methylthio)phenyl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]- naphthalene-2,7-dione (2i) 84 yield%; 62.2 mg 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 3H), (m, 2H), 6.95 (d, J = 7.6 Hz, 2H), 6.65 (d, J = 7.6 Hz, 2H), 3.61 (d, J = 5.6 Hz, 1H), 3.37 (d, J = 5.2 Hz, 1H), 2.39 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 192.6, 190.9, 138.1, 134.5, 134.2, 132.4, 131.8, 131.5, 130.0, 128.4, 128.2, 128.1, 126.8, 125.7, 50.9, 42.7, 40.2, 15.4; LRMS (EI, 70 ev) m/z (%): 370 (M +, 100), 326 (18), 279 (51); HRMS (ESI): calculated for C24H19O2S [M+H + ] , found

12 dione (2j) 95% yield, 68.0 mg; 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 5H), 7.06 (d, J = 8.0 Hz, 2H), 6.67 (d, J = 8.0 Hz, 2H), 3.61 (d, J = 5.2 Hz, 1H), 3.38 (d, J = 5.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 192.3, 190.7, 134.5, 134.3, 133.4, 132.3, 132.3, 132.0, 131.8, 131.2, 129.2, 128.2, 128.2, 128.2, 128.1, 126.8, 50.6, 42.1, 39.9; LRMS (EI, 70 ev) m/z (%): 360 (M + +2, 36), 358 (M +, 100), 323 (15); HRMS (ESI): calculated for C23H16 35 ClO2 [M+H + ] , found dione (2k) 54% yield, 39.8 mg; 1 H NMR (400 MHz, CDCl3) δ (m, 2H), 7.95 (d, J = 8.4 Hz, 2H), (m, 2H), (m, 3H), (m, 2H), 6.91 (d, J = 8.8 Hz, 2H), 3.72 (d, J = 5.6 Hz, 1H), 3.48 (d, J = 5.6 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 191.6, 190.1, 147.0, 141.1, 134.8, 134.5, 132.2, 132.1, 131.7, 130.6, 128.7, 128.6, 128.4, 128.2, 126.9, 123.2, 50.8, 41.5, 40.0; LRMS (EI, 70 ev) m/z (%): 369 (M +, 100), 339 (10), 278 (39); HRMS (ESI): calculated for C23H16NO4 [M+H + ] , found (4-Chlorophenyl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-1-(4-Nitrophenyl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-1-(2-Bromophenyl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7- dione (2l) 84 yield%, 67.5 mg; 1 H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 6.4 Hz, 1H), 8.11 (d, J = 7.6 Hz, 1H), (m, 2H), 7.51 (d, J = 7.2 Hz, 1H), (m, 5H), (m, 2H), 6.64 (d, J = 7.6 Hz, 1H), 3.81 (d, J = 6.0 Hz, 1H), 3.74 (d, J = 6.0 Hz,

13 1H); 13 C NMR (100 MHz, CDCl3) δ 192.7, 190.8, 134.6, 134.2, 132.7, 132.6, 132.5, 132.4, 131.5, 131.2, 129.0, 128.1, 128.0, 128.0, 127.6, 127.1, 126.7, 126.3, 49.4, 43.6, 37.7; LRMS (EI, 70 ev) m/z (%): 404 (M + +2, 96), 402 (M +, 100), 323 (60), 265 (58); HRMS (ESI): calculated for C23H16 79 BrO2 [M+H + ] , found (Naphthalen-1-yl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7- dione (2m) 5 86% yield, 64.3 mg; 1 H NMR (400 MHz, CDCl3) δ 8.30 (d, J = 7.2 Hz, 1H), 8.14 (d, J = 7.2 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), (m, 3H), 7.61 (d, J = 8.4 Hz, 1H), 7.57 (t, J = 7.6 Hz, 1H), 7.49 (t, J = 7.6 Hz, 1H), 7.13 (t, J = 7.6 Hz, 1H), (m, 6H), 4.01 (d, J = 5.6 Hz, 1H), 3.97 (d, J = 6.0 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 193.0, 191.5, 134.5, 134.3, 133.3, 132.7, 132.6, 132.5, 131.7, 130.9, 128.8, 128.8, 128.5, 128.1, 127.8, 127.7, 126.8, 126.8, 126.0, 125.0, 124.3, 123.0, 50.2, 41.1, 37.5; LRMS (EI, 70 ev) m/z (%): 374 (M +, 100), 357 (10), 329 (51). 1-(Furan-2-yl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2n) 38% yield, 23.9 mg; 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 5H), 7.10 (s, 1H), (m, 1H), (m, 1H), 3.64 (d, J = 5.6 Hz, 1H), 3.44 (d, J = 5.2 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 192.1, 190.6, 147.6, 142.2, 134.5, 134.3, 132.4, 132.2, 131.1, 128.1, 128.0, 126.8, 110.6, 108.9, 49.4, 38.9, 35.8; LRMS (EI, 70 ev) m/z (%): 314 (M +, 100), 285 (16), 257 (24); HRMS (ESI): calculated for C21H15O3 [M+H + ] , found

14 (E)-1a-phenyl-1-styryl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2o) 80% yield, 56.0 mg ; 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 5H), (m, 3H), 7.11 (d, J = 7.2 Hz, 2H), 6.61 (d, J = 15.6 Hz, 1H), 5.32 (dd, J = 15.6, 9.2 Hz, 1H), 3.28 (d, J = 4.8 Hz, 1H), 3.06 (t, J = 9.2, 4.8 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 192.0, 191.1, 136.1, 134.4, 134.2, 132.5, 132.4, 132.4, 131.5, 128.6, 128.4, 128.3, 127.9, 126.7, 126.2, 125.1, 49.1, 42.6, 41.5; LRMS (EI, 70 ev) m/z (%): 350 (M +, 100), 331 (14), 259 (53); HRMS (ESI): calculated for C25H19O2 [M+H + ] , found Butyl-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2p) 40% yield, 24.3 mg; 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 5H), 2.92 (d, J = 5.2 Hz, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 193.6, 192.2, 134.1, 133.9, 132.8, 132.6, 132.4, 131.2, 128.2, 128.0, 127.8, 126.5, 48.4, 40.7, 40.4, 30.9, 29.9, 22.2, 13.8; LRMS (EI, 70 ev) m/z (%): 304 (M +, 100), 261 (42), 247 (47); HRMS (ESI): calculated for C21H21O2 [M+H + ] , found a-Methyl-7a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2q) 79% yield; 41.4 mg 1 H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 7.2 Hz, 1H), 7.99 (d, J = 7.2 Hz, 1H), (m, 2H), (m, 3H), 7.25 (d, J = 7.2 Hz, 2H), 2.22 (d, J = 4.8 Hz, 1H), 2.01 (d, J = 4.8 Hz, 1H), 1.23 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 195.6, 194.4, 134.0, 133.9, 133.7, 132.5, 132.1, 128.6, 128.1, 127.0, 126.7, 48.4, 38.9, 32.3, 15.4; LRMS (EI, 70 ev) m/z (%): 262 (M +, 75), 247 (100), 233 (46); HRMS (ESI):

15 calculated for C18H15O2 [M+H + ] , found Methyl-1,1a-diphenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2r) 94 yield%, 63.5 mg; 1 H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 8.0 Hz, 1H), 7.96 (s, 1H), 7.59 (d, J = 8.0 Hz, 1H), (m, 3H), (m, 5H), 6.74 (d, J = 7.2 Hz, 2H), 3.63 (d, J = 5.6 Hz, 1H), 3.39 (d, J = 5.6 Hz, 1H), 2.51 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 192.7, 191.3, 145.7, 135.1, 133.4, 132.4, 131.9, 131.7, 130.1, 128.2, 128.0, 128.0, 127.9, 127.4, 126.9, 50.8, 43.2, 39.8, 21.9; LRMS (EI, 70 ev) m/z (%): 338 (M +, 100), 323 (16), 279 (35); HRMS (ESI): calculated for C24H19O2 [M+H + ] , found Nitro-1,1a-diphenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2s) 82% yield, 60.7 mg; 1 H NMR (400 MHz, CDCl3) δ 8.92 (s, 1H), 8.57 (d, J = 8.4 Hz, 1H), 8.37 (d, J = 8.4 Hz, 1H), (m, 3H), (m, 5H), 6.75 (d, J = 7.6 Hz, 2H), 3.78 (d, J = 5.2 Hz, 1H), 3.44 (d, J = 5.6 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 190.3, 189.4, 151.4, 136.3, 133.8, 132.4, 131.7, 130.7, 130.2, 128.4, 128.3, 128.2, 128.2, 128.0, 127.9, 122.4, 51.4, 42.7, 40.3; LRMS (EI, 70 ev) m/z (%): 369 (M +, 100), 322 (19), 265 (29); HRMS (ESI): calculated for C23H16NO4 [M+H + ] , found ,7-Dioxo-1,7a-diphenyl-1a,2,7,7a-tetrahydro-1H-cyclopropa[b]naphthalen-4-yl acetate (2t) 76% yield, 58.0 mg; 1 H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 8.4 Hz, 1H), 7.82 (s, 1H), 7.50 (d, J = 8.8 Hz, 1H), (m, 3H), (m, 5H), 6.75 (d, J = 7.2 Hz, 2H),

16 3.66 (d, J = 5.6 Hz, 1H), 3.46 (d, J = 5.6 Hz, 1H), 2.36 (s, 3H); 13 C NMR (100 MHz, CDCl3) δ 191.6, 190.0, 168.6, 155.3, 134.2, 133.1, 131.8, 131.4, 130.2, 130.0, 128.0, 128.0, 127.8, 127.6, 119.6, 50.8, 42.9, 40.1, 21.0; LRMS (EI, 70 ev) m/z (%): 382 (M +, 100), 340 (93), 295 (31); HRMS (ESI): calculated for C25H19O4 [M+H + ] , found (C) References (1) Wang, Z.-Q.; Zhang, W.-W.; Gong, L.-B.; Tang, R.-Y.; Yang, X.-H.; Liu, Y.; Li, J.- H. Angew. Chem. Int. Ed. 2011, 50, (2) Wang, Y.-H.; Zhu, L.-L.; Zhang, Y.-X.; Chen, Z. Chem. Commun. 2010, 46, 577. (3) Liang, G.; Xu, Y.; Seiple, I. B.; Trauner, D. J. Am. Chem. Soc. 2006, 128, (4) Petrone, D. A.; Malik, H. A.; Clemenceau, A.; Lautens, M. Org. Lett. 2012, 14, (5) Zheng, L.; Zhou, B.; Jin, H.; Li, T.; Liu, Y. Org. Lett. 2018, 20, DOI: /acs.orglett.8b03007.

17 (D) Spectra 1,1a-Diphenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2a)

18 Phenyl-1a-(p-tolyl)-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2b)

19 1a-(4-Chlorophenyl)-1-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7- dione (2c) Cl O O Cl O O

20 Methyl 4-(2,7-dioxo-1-phenyl-1,2,7,7a-tetrahydro-1aH-cyclopropa[b]naphthalen- 1a-yl)-3-methylbenzoate (2d) COOMe O O COOMe O O

21 1a-Cyclopropyl-1-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2e)

22 1a-Butyl-1-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2f)

23 2-(2,7-Dioxo-1-phenyl-1,2,7,7a-tetrahydro-1aH-cyclopropa[b]naphthalen-1ayl)ethyl benzoate (2g)

24 1a-Phenyl-1-(p-tolyl)-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2h) O O O O

25 1-(4-(Methylthio)phenyl)-1a-phenyl-1a,7a-dihydro-1Hcyclopropa[b]naphthalene-2,7-dione (2i)

26 1-(4-Chlorophenyl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7- dione (2j)

27 1-(4-Nitrophenyl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7- dione (2k)

28 1-(2-Bromophenyl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7- dione (2l)

29 1-(Naphthalen-1-yl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7- dione (2m)

30 1-(Furan-2-yl)-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2n)

31 (E)-1a-phenyl-1-styryl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2o)

32 1-Butyl-1a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2p)

33 1a-Methyl-7a-phenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2q) O O O O

34 4-Methyl-1,1a-diphenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2r)

35 5-Nitro-1,1a-diphenyl-1a,7a-dihydro-1H-cyclopropa[b]naphthalene-2,7-dione (2s)

36 HSQC HMBC

37 NOE

38 2,7-Dioxo-1,7a-diphenyl-1a,2,7,7a-tetrahydro-1H-cyclopropa[b]naphthalen-4-yl acetate (2t) O Ph AcO O Ph O Ph AcO O Ph

39 (E) The X-ray single-crystal diffraction analysis of 2m (CCDC ): Table S1. Crystal data and structure refinement for ljh053_0m. Identification code Empirical formula ljh053_0m C27 H18 O2 Formula weight Temperature Wavelength Crystal system, space group 296(2) K A Monoclinic, P2(1)/c Unit cell dimensions a = (2) A alpha = 90 deg. b = (2) A c = (3) A beta = (3) deg. gamma = 90 deg. Volume (6) A^3 Z, Calculated density 4, Mg/m^3 Absorption coefficient mm^-1 F(000) 784 Crystal size 0.23 x 0.21 x 0.20 mm

40 Theta range for data collection Limiting indices 1.58 to deg. -16<=h<=16, -13<=k<=13, -17<=l<=10 Reflections collected / unique / 4242 [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 4242 / 0 / 263 Goodness-of-fit on F^ Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient (9) Largest diff. peak and hole and e.a^-3 Table S2. Atomic coordinates ( x 10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for ljh053_0m. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) O(2) 1136(1) -690(1) 782(1) 75(1) O(1) 4295(1) 2270(1) 1950(1) 72(1) C(24) 3464(2) 6066(2) -1609(1) 62(1) C(23) 2416(2) 6064(2) -1732(1) 60(1) C(22) 1801(1) 5149(1) -1303(1) 49(1) C(27) 2302(1) 4203(1) -721(1) 40(1) C(18) 1684(1) 3277(1) -287(1) 40(1) C(3) 2221(1) 2221(1) 241(1) 38(1) C(2) 2556(1) 2265(1) 1319(1) 38(1) C(1) 3598(1) 1684(1) 1539(1) 43(1) C(11) 3772(1) 372(1) 1220(1) 44(1)

41 C(10) 4779(1) -101(2) 1304(1) 55(1) C(9) 4970(2) -1328(2) 1067(1) 66(1) C(21) 713(2) 5132(2) -1443(1) 65(1) C(20) 142(1) 4251(2) -1027(1) 65(1) C(19) 627(1) 3308(2) -441(1) 52(1) C(4) 1687(1) 1397(1) 941(1) 42(1) C(5) 1861(1) 34(2) 868(1) 49(1) C(6) 2956(1) -410(1) 895(1) 46(1) C(8) 4173(2) -2086(2) 729(1) 73(1) C(7) 3168(2) -1644(2) 643(1) 63(1) C(12) 2300(1) 3380(1) 1918(1) 39(1) C(17) 1569(1) 3291(1) 2602(1) 45(1) C(16) 1372(1) 4306(2) 3189(1) 53(1) C(15) 1905(1) 5404(2) 3100(1) 57(1) C(14) 2635(1) 5508(2) 2421(1) 59(1) C(13) 2830(1) 4503(2) 1834(1) 52(1) C(26) 3398(1) 4230(1) -615(1) 45(1) C(25) 3957(1) 5130(2) -1048(1) 54(1) Table S3. Bond lengths [A] and angles [deg] for ljh053_0m. O(2)-C(5) (18) O(1)-C(1) (17) C(24)-C(23) 1.351(3) C(24)-C(25) 1.397(2) C(24)-H(24) C(23)-C(22) 1.411(2) C(23)-H(23) C(22)-C(21) 1.403(2) C(22)-C(27) 1.424(2)

42 C(27)-C(26) 1.411(2) C(27)-C(18) 1.424(2) C(18)-C(19) 1.366(2) C(18)-C(3) (19) C(3)-C(4) 1.507(2) C(3)-C(2) (19) C(3)-H(3) C(2)-C(1) 1.494(2) C(2)-C(12) (19) C(2)-C(4) (19) C(1)-C(11) 1.488(2) C(11)-C(10) 1.390(2) C(11)-C(6) 1.395(2) C(10)-C(9) 1.374(2) C(10)-H(10) C(9)-C(8) 1.368(3) C(9)-H(11) C(21)-C(20) 1.345(3) C(21)-H(21) C(20)-C(19) 1.415(2) C(20)-H(20) C(19)-H(19) C(4)-C(5) 1.474(2) C(4)-H(4) C(5)-C(6) 1.487(2) C(6)-C(7) 1.392(2) C(8)-C(7) 1.377(3) C(8)-H(8) C(7)-H(7)

43 C(12)-C(17) 1.382(2) C(12)-C(13) 1.387(2) C(17)-C(16) 1.388(2) C(17)-H(17) C(16)-C(15) 1.366(2) C(16)-H(16) C(15)-C(14) 1.377(2) C(15)-H(15) C(14)-C(13) 1.378(2) C(14)-H(14) C(13)-H(13) C(26)-C(25) 1.361(2) C(26)-H(26) C(25)-H(25) C(23)-C(24)-C(25) (16) C(23)-C(24)-H(24) C(25)-C(24)-H(24) C(24)-C(23)-C(22) (16) C(24)-C(23)-H(23) C(22)-C(23)-H(23) C(21)-C(22)-C(23) (16) C(21)-C(22)-C(27) (16) C(23)-C(22)-C(27) (15) C(26)-C(27)-C(22) (14) C(26)-C(27)-C(18) (13) C(22)-C(27)-C(18) (13) C(19)-C(18)-C(27) (14) C(19)-C(18)-C(3) (14) C(27)-C(18)-C(3) (12)

44 C(18)-C(3)-C(4) (12) C(18)-C(3)-C(2) (12) C(4)-C(3)-C(2) 59.95(9) C(18)-C(3)-H(3) C(4)-C(3)-H(3) C(2)-C(3)-H(3) C(1)-C(2)-C(12) (11) C(1)-C(2)-C(4) (12) C(12)-C(2)-C(4) (12) C(1)-C(2)-C(3) (11) C(12)-C(2)-C(3) (11) C(4)-C(2)-C(3) 59.04(9) O(1)-C(1)-C(11) (14) O(1)-C(1)-C(2) (14) C(11)-C(1)-C(2) (12) C(10)-C(11)-C(6) (15) C(10)-C(11)-C(1) (14) C(6)-C(11)-C(1) (13) C(9)-C(10)-C(11) (17) C(9)-C(10)-H(10) C(11)-C(10)-H(10) C(8)-C(9)-C(10) (17) C(8)-C(9)-H(11) C(10)-C(9)-H(11) C(20)-C(21)-C(22) (16) C(20)-C(21)-H(21) C(22)-C(21)-H(21) C(21)-C(20)-C(19) (16) C(21)-C(20)-H(20) 119.7

45 C(19)-C(20)-H(20) C(18)-C(19)-C(20) (16) C(18)-C(19)-H(19) C(20)-C(19)-H(19) C(5)-C(4)-C(3) (13) C(5)-C(4)-C(2) (13) C(3)-C(4)-C(2) 61.01(9) C(5)-C(4)-H(4) C(3)-C(4)-H(4) C(2)-C(4)-H(4) O(2)-C(5)-C(4) (15) O(2)-C(5)-C(6) (15) C(4)-C(5)-C(6) (13) C(7)-C(6)-C(11) (15) C(7)-C(6)-C(5) (15) C(11)-C(6)-C(5) (13) C(9)-C(8)-C(7) (17) C(9)-C(8)-H(8) C(7)-C(8)-H(8) C(8)-C(7)-C(6) (18) C(8)-C(7)-H(7) C(6)-C(7)-H(7) C(17)-C(12)-C(13) (14) C(17)-C(12)-C(2) (13) C(13)-C(12)-C(2) (13) C(12)-C(17)-C(16) (15) C(12)-C(17)-H(17) C(16)-C(17)-H(17) C(15)-C(16)-C(17) (15)

46 C(15)-C(16)-H(16) C(17)-C(16)-H(16) C(16)-C(15)-C(14) (15) C(16)-C(15)-H(15) C(14)-C(15)-H(15) C(15)-C(14)-C(13) (16) C(15)-C(14)-H(14) C(13)-C(14)-H(14) C(14)-C(13)-C(12) (15) C(14)-C(13)-H(13) C(12)-C(13)-H(13) C(25)-C(26)-C(27) (14) C(25)-C(26)-H(26) C(27)-C(26)-H(26) C(26)-C(25)-C(24) (16) C(26)-C(25)-H(25) C(24)-C(25)-H(25) Symmetry transformations used to generate equivalent atoms: Table S4. Anisotropic displacement parameters (A^2 x 10^3) for ljh053_0m. The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U h k a* b* U12 ] U11 U22 U33 U23 U13 U12 O(2) 66(1) 52(1) 107(1) -3(1) 1(1) -22(1) O(1) 50(1) 66(1) 98(1) -22(1) -24(1) 3(1) C(24) 88(1) 47(1) 50(1) 4(1) 2(1) -9(1) C(23) 94(1) 40(1) 46(1) 5(1) -5(1) 9(1) C(22) 63(1) 44(1) 40(1) -5(1) -6(1) 13(1) C(27) 48(1) 37(1) 34(1) -5(1) -4(1) 7(1)

47 C(18) 39(1) 43(1) 36(1) -8(1) -3(1) 7(1) C(3) 37(1) 39(1) 37(1) -3(1) 0(1) 2(1) C(2) 38(1) 38(1) 38(1) -1(1) 1(1) -1(1) C(1) 43(1) 44(1) 43(1) 0(1) -1(1) 0(1) C(11) 51(1) 44(1) 36(1) 5(1) 2(1) 6(1) C(10) 57(1) 59(1) 48(1) 5(1) 1(1) 14(1) C(9) 72(1) 67(1) 60(1) 6(1) 7(1) 27(1) C(21) 68(1) 65(1) 60(1) 4(1) -12(1) 24(1) C(20) 44(1) 85(1) 64(1) -8(1) -10(1) 23(1) C(19) 42(1) 61(1) 50(1) -6(1) -2(1) 7(1) C(4) 38(1) 44(1) 45(1) -3(1) 1(1) -4(1) C(5) 56(1) 44(1) 47(1) 1(1) 1(1) -10(1) C(6) 59(1) 40(1) 40(1) 3(1) 2(1) 2(1) C(8) 98(2) 51(1) 70(1) -2(1) 8(1) 26(1) C(7) 84(1) 44(1) 60(1) -2(1) 0(1) 3(1) C(12) 41(1) 41(1) 36(1) 0(1) -3(1) 2(1) C(17) 49(1) 46(1) 39(1) 4(1) 1(1) 3(1) C(16) 64(1) 59(1) 38(1) 2(1) 6(1) 15(1) C(15) 80(1) 46(1) 46(1) -8(1) -2(1) 14(1) C(14) 73(1) 42(1) 60(1) -8(1) -1(1) -5(1) C(13) 55(1) 48(1) 52(1) -6(1) 6(1) -5(1) C(26) 50(1) 43(1) 42(1) 1(1) -2(1) 3(1) C(25) 59(1) 53(1) 51(1) 0(1) 4(1) -6(1) Table S5. Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for ljh053_0m. x y z U(eq) H(24) H(23)

48 H(3) H(10) H(11) H(21) H(20) H(19) H(4) H(8) H(7) H(17) H(16) H(15) H(14) H(13) H(26) H(25) Table S6. Torsion angles [deg] for ljh053_0m. C(25)-C(24)-C(23)-C(22) 0.5(3) C(24)-C(23)-C(22)-C(21) (16) C(24)-C(23)-C(22)-C(27) 0.3(2) C(21)-C(22)-C(27)-C(26) (14) C(23)-C(22)-C(27)-C(26) -0.7(2) C(21)-C(22)-C(27)-C(18) -0.8(2) C(23)-C(22)-C(27)-C(18) (13) C(26)-C(27)-C(18)-C(19) (14) C(22)-C(27)-C(18)-C(19) 0.4(2) C(26)-C(27)-C(18)-C(3) -5.1(2) C(22)-C(27)-C(18)-C(3) (12)

49 C(19)-C(18)-C(3)-C(4) -23.3(2) C(27)-C(18)-C(3)-C(4) (12) C(19)-C(18)-C(3)-C(2) (17) C(27)-C(18)-C(3)-C(2) 89.78(16) C(18)-C(3)-C(2)-C(1) (13) C(4)-C(3)-C(2)-C(1) (13) C(18)-C(3)-C(2)-C(12) 3.37(19) C(4)-C(3)-C(2)-C(12) (14) C(18)-C(3)-C(2)-C(4) (15) C(12)-C(2)-C(1)-O(1) -21.2(2) C(4)-C(2)-C(1)-O(1) (15) C(3)-C(2)-C(1)-O(1) (16) C(12)-C(2)-C(1)-C(11) (13) C(4)-C(2)-C(1)-C(11) 10.50(19) C(3)-C(2)-C(1)-C(11) (17) O(1)-C(1)-C(11)-C(10) -7.6(2) C(2)-C(1)-C(11)-C(10) (13) O(1)-C(1)-C(11)-C(6) (16) C(2)-C(1)-C(11)-C(6) -12.6(2) C(6)-C(11)-C(10)-C(9) 0.1(2) C(1)-C(11)-C(10)-C(9) (15) C(11)-C(10)-C(9)-C(8) 1.2(3) C(23)-C(22)-C(21)-C(20) (17) C(27)-C(22)-C(21)-C(20) 0.9(3) C(22)-C(21)-C(20)-C(19) -0.5(3) C(27)-C(18)-C(19)-C(20) 0.0(2) C(3)-C(18)-C(19)-C(20) (14) C(21)-C(20)-C(19)-C(18) 0.1(3) C(18)-C(3)-C(4)-C(5) (14)

50 C(2)-C(3)-C(4)-C(5) (14) C(18)-C(3)-C(4)-C(2) (14) C(1)-C(2)-C(4)-C(5) 4.4(2) C(12)-C(2)-C(4)-C(5) (14) C(3)-C(2)-C(4)-C(5) (15) C(1)-C(2)-C(4)-C(3) (13) C(12)-C(2)-C(4)-C(3) (14) C(3)-C(4)-C(5)-O(2) (16) C(2)-C(4)-C(5)-O(2) (15) C(3)-C(4)-C(5)-C(6) 53.14(18) C(2)-C(4)-C(5)-C(6) -17.6(2) C(10)-C(11)-C(6)-C(7) -1.2(2) C(1)-C(11)-C(6)-C(7) (14) C(10)-C(11)-C(6)-C(5) (13) C(1)-C(11)-C(6)-C(5) -1.1(2) O(2)-C(5)-C(6)-C(7) 11.9(2) C(4)-C(5)-C(6)-C(7) (15) O(2)-C(5)-C(6)-C(11) (16) C(4)-C(5)-C(6)-C(11) 16.1(2) C(10)-C(9)-C(8)-C(7) -1.5(3) C(9)-C(8)-C(7)-C(6) 0.4(3) C(11)-C(6)-C(7)-C(8) 1.0(3) C(5)-C(6)-C(7)-C(8) (16) C(1)-C(2)-C(12)-C(17) (15) C(4)-C(2)-C(12)-C(17) 40.18(19) C(3)-C(2)-C(12)-C(17) (15) C(1)-C(2)-C(12)-C(13) 67.81(18) C(4)-C(2)-C(12)-C(13) (14) C(3)-C(2)-C(12)-C(13) (17)

51 C(13)-C(12)-C(17)-C(16) 0.2(2) C(2)-C(12)-C(17)-C(16) (13) C(12)-C(17)-C(16)-C(15) -0.5(2) C(17)-C(16)-C(15)-C(14) 0.6(2) C(16)-C(15)-C(14)-C(13) -0.3(3) C(15)-C(14)-C(13)-C(12) 0.0(3) C(17)-C(12)-C(13)-C(14) 0.1(2) C(2)-C(12)-C(13)-C(14) (14) C(22)-C(27)-C(26)-C(25) 0.3(2) C(18)-C(27)-C(26)-C(25) (14) C(27)-C(26)-C(25)-C(24) 0.4(2) C(23)-C(24)-C(25)-C(26) -0.9(3) Symmetry transformations used to generate equivalent atoms:

Copper(II) Ionic Liquid Catalyzed Cyclization-Aromatization of. Hydrazones with Dimethyl Acetylenedicarboxylate: A Green Synthesis

Copper(II) Ionic Liquid Catalyzed Cyclization-Aromatization of Hydrazones with Dimethyl Acetylenedicarboxylate: A Green Synthesis of Fully Substituted Pyrazoles Shirin Safaei, Iraj Mohammadpoor-Baltork,*