Supporting Information

Supporting Information Palladium-catalyzed Tandem Reaction of Three Aryl Iodides Involving Triple C-H Activation Xiai Luo, a,b Yankun Xu, a Genhua Xiao, a Wenjuan Liu, a Cheng Qian, a Guobo Deng, a Jianxin Song, a Yun Liang a * and Chunming Yang a * a ational & Local Joint Engineering Laboratory for ew Petro-chemical Materials and Fine Utilization of Resources, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education, Key Laboratory of the Assembly and Application of rganic Functional Molecules, Hunan ormal University, Changsha, Hunan 410081, China b Hunan University of Medicine, Huaihua, 418000, China E-mail: yliang@hunnu.edu.cn; chunmingyang@126.com

Supporting Information List of Contents (A) General Information... 2 (B) ptimized Reaction Conditions... 5 (C) Mechanistic Studies... 6 (D) Analytical Data... 10 (E) Reference... 30 (F) Spectra... 31 (G) The X-ray Single-Crystal Diffraction Analysis of 3ac.... 59 1

(A) General Information 1 H-MR and 13 C-MR spectra were recorded at room temperature using a Bruker Avance-500 instruments ( 1 H MR at 500 MHz and 13 C MR at 125 MHz), MR spectra of all products were reported in ppm with reference to solvent signals [ 1 H MR: CD(H)Cl 3 (7.26 ppm), 13 C MR: CD(H)Cl 3 (77.00 ppm)]. Signal patterns are indicated as s, singlet; d, doublet; t, triplet, and m, multiplet. HPLC/Q-TF-MS analysis was performed with an Agilent 1290 LC system coupled with a 6530Q-TF/MS accurate-mass spectrometer (Agilent Technologies, USA).The mass spectrometry was performed in the positive electrospray ionization (ESI+) mode. Reactions were monitored by thin-layer chromatography Column chromatography (petroleum ether/ethyl acetate) was performed on silica gel (200-300 mesh). Analytical grade solvents and commercially available reagents were purchased from commercial sources and used directly without further purification unless otherwise stated. [1], [2] (a) Synthesis of Starting Materials General Procedures 1 (GP1): Step I:A 50 ml round bottom flask equipped with a stir bar was charged with 2-phenylacetic acid derivatives (20 mmol, 1.0 equiv.), concentrated sulfuric acid (3 drops), and ethanol (20 ml), the mixture was heated to reflux for 6 hours. After that, the reaction mixture was allowed to cool down to room temperature. After the methanol was removed by rotary evaporation, the residue was diluted with ethyl acetate and treated with saturated sodium bicarbonate solution and brine. The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuoto afford the corresponding methyl 2-phenylacetate derivatives. Step II: To a solution of methyl phenylacetate derivatives (20 mmol) in anhydrous toluene (40 ml), K 2 C 3 (30 mmol), tetrabutylammonium bisulfate (2.0 mmol), and 2

formaldehyde (30 mmol) were added. The reaction mixture was heated at 80 C for 12 h, quenched with H 2 (100 ml), and extracted with EA (3 50 ml). The combined organic layers were dried over a 2 S 4 and concentrated under reduced pressure to afford the desired product as a colorless oil. Step III: To a solution of prepared methyl 2-phenylacrylate derivatives in THF (10 ml), a solution of potassium hydrate (4.49 g, 80 mmol, 4.0 equiv.) in water (10 ml) was added. The reaction mixture was heated at reflux for 2 hours and then cooled to 0 o C. Addition of concentrated hydrochloric acid resulted in precipitation of a white solid, which was extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo to afford 2-phenylacrylic acid derivatives, which was used directly in the next step. General Procedures 2 (GP2): Step I:xalyl chloride (2 equiv) was added to a solution of substituted 2-phenylacrylic acid (1.0 equiv)and DMF (4 drops) in CH 2 Cl 2 at 0 C drop-wise. The reaction was maintain at 0 o C for about 5 minutes and then allowed to warm to room temperature and was stirred for 1 hour. The excess oxalyl chloride was removed under vacuum and the resulting crude acid chloride used in next step directly. Step II: A solution of the substituted 2-iodoaniline (1.0 equiv), DMAP (0.05 equiv) and TEA (2.0 equiv) was prepared in CH 2 Cl 2 (2mL) and cooled to 0 o C. The acyl chloride solution was added dropwise into the solution. After 5 minutes, the reaction was allowed to warm to room temperature and was stirred overnight. The reaction was quenched with saturated ahc 3 solution and extracted with CH 2 Cl 2 twice. The combined organic layers were washed with brine, dried over a 2 S 4 and concentrated in vacuo. The resulting crude amide was used in next step without further purification. Step III:aH (80 mg, 60% in mineral oil, 2.0 mmol, 2.0 equiv) was added to a solution of the above product in THF (5.0 ml) at 0 o C in portions. After stirring for 3

20 min at 0 o C, alkyl/benzyl halide (3.0 mmol, 3.0 equiv) was added dropwise and the reaction mixture was allowed to room temperature and stirred for another 2 h. After completion of the reaction (monitored by TLC), the residue was quenched with water and extracted into ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and the solution was evaporated to dryness. The crude product was purified by column chromatography (petroleum ether : ethyl acetate = 10:1) to provide the desired products1a-1p and 4. (b) Typical Procedures The mixture of -(2-iodophenyl)--benzyl-2-phenylacrylamide 1 (0.2 mmol), Iodobenzene2 (0.8 mmol, 4.0 equiv), Pd(Ac) 2 (0.02 mmol, 10 mol % ), PPh 3 (0.04 mmol, 20 mol %), and Cs 2 C 3 (1.0 mmol, 5.0 equiv) in DMS (2 ml) was stirred under nitrogen atmosphere at 120 C for 12 h. After the completion of the reaction (monitored by TLC), the reaction mixture was filtered and the filtrate was washed by H 2 and saturated salt solution and then evaporated under reduced pressure, the crude product was purified by column chromatography (petroleum ether : ethyl acetate = 10:1) to provide the desired products 3. Typical procedures of products 5 are same as products 3. 4

(B)ptimized Reaction Conditions Table S1. ptimized reaction conditions [a] Entry Catalyst Ligand Base Solvent Yield (%) 1 Pd(Ac) 2 PPh 3 K 2 C 3 DMS 35 2 Pd(Ac) 2 PPh 3 Cs 2 C 3 DMS 45 3 Pd(Ac) 2 PPh 3 K 3 P 4 DMS 28 4 Pd(Ac) 2 PPh 3 K t Bu 3 DMS Trace 5 Pd(PPh 3 ) 4 PPh 3 Cs 2 C 3 DMS 21 6 Pd(dba) 2 PPh 3 Cs 2 C 3 DMS 31 7 [PdCl(allyl PPh 3 Cs 2 C 3 DMS 42 )] 2 8 Pd(Ac) 2 Cs 2 C 3 DMS 32 9 Pd(Ac) 2 P t Bu 3 Cs 2 C 3 DMS 35 10 Pd(Ac) 2 P(o-tol) 3 Cs 2 C 3 DMS 28 11 Pd(Ac) 2 XPhos Cs 2 C 3 DMS 34 12 Pd(Ac) 2 PPh 3 Cs 2 C 3 DMF 36 13 Pd(Ac) 2 PPh 3 Cs 2 C 3 Toluene trace 14 Pd(Ac) 2 PPh 3 Cs 2 C 3 Dioxane trace 15 Pd(Ac) 2 PPh 3 Cs 2 C 3 DMAc 40 16 [b] Pd(Ac) 2 PPh 3 Cs 2 C 3 DMS 65 17 [c] Pd(Ac) 2 PPh 3 Cs 2 C 3 DMS 45 18 [d] Pd(Ac) 2 PPh 3 Cs 2 C 3 DMS 44 [a] 1a (0.2 mmol), 2a (0.8 mmol), palladium catalyst (10 mol%), Ligand (20 mol%), base (5 equiv), additive (0.1 mmol), solvent (2 ml) at 120 o C under nitrogen atmosphere for 12 h. Yields of isolated are given. [b] TBAI. [c] TBAB. [d] TBAC. 5

(C) Mechanistic Studies (a) Investigation of the reaction was initiated by the spiropalladcycle 5 [3] To a flame dried 2 dram vial cooled under nitrogen, -(2-iodophenyl)--methyl-2-phenylacrylamide 1a (72.6 mg, 0.2 mmol, 1 equiv), Pd(PPh 3 ) 4 (231 mg, 0.2 mmol, 1 equiv), and Cs 2 C 3 (97.7 mg, 0.3 mmol, 1.5 equiv) were added and allowed to purge for 10 minutes. PhMe (2 ml, 0.1 M) was added and a teflon line screw cap was fitted on the two dram vial, sealed with Teflon tape and place in a preheated oil bath at 80 C for 12 hours. The reaction mixture was cooled to room temperature. nce cooled, the reaction was passed through a plug of celite using DCM and concentrated in vacuo. nce solidified, hexane was used to triturate the compound. The mixture was passed through glass wool and the collected solid was redissolved in DCM and concentrated in vacuo. The palladacycle4 then recrystallized Et 2 and hexanes to obtain a pale yellow solid (86.6 mg, 0.1 mmol, 50%). The mixture of palladacycle 4 (86.6 mg, 0.1 mmol, 1 equiv), Iodobenzene 2a (81.6 mg, 0.4 mmol, 4.0 equiv), Cs 2 C 3 (162.9 mg, 0.5 mmol, 5 equiv), TBAI (18.5 mg, 0.05 mmol, 0.5 equiv) in DMS (1 ml) was stirred under nitrogen atmosphere at 120 C for 12 h. After the completion of the reaction (monitored by TLC), the reaction mixture was filtered and the filtrate was washed by H 2 and saturated salt solution and then evaporated under reduced pressure, the crude product was purified by column chromatography (petroleum ether : ethyl acetate = 10:1) to provide the desired products 3aa as a white solid(16 mg, 42%). 6

(b) Investigation of the reaction underwent a phenylation first and followed by an insertion of iodobenzene [3],[4] CH (I)MeH,reflux6h CMe I (II)PhB(H) 2,DMA 80 o C,5h i ii (II)Bu 4 HS 4,HCH, K 2 C 3,toluene,80 o C,8h CH (I)(CCl) 2,DMF(cat), DCM,0 o Ctort,2h (III)KH,THF/H 2,reflux,2h (II) arylamines, DMAP, TEA,DCM,0 o Ctort (III) MeI, ah, THF,0 o Ctort,12h I Me 5 2-(2-iodophenyl)acetic acid (3.93 g, 15mmol), MeH (15 ml) and 2 drops of H 2 S 4 were added into a round bottomed flask. The mixture was heated to reflux for 6 hours. After that, the reaction mixture was allowed to cool down to room temperature. After the methanol was removed by rotary evaporation, the residue was diluted with ethyl acetate and treated with saturated sodium bicarbonate solution and brine. The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuoto afford the corresponding methyl 2-(2-iodophenyl)acetate. Water (4.0mL) and DME (30.0 ml) were poured into a round bottomed flask, fitted with a condenser and nitrogen flow, and bubbled through with nitrogen. Potassium carbonate (3.45 g, 25 mmol), methyl 2-(2-iodophenyl)acetate (2.76 g, 10.0 mmol), substituted phenylboronic acid (10.5 mmol), and bis(triphenylphosphine)palladium(ii) chloride (105 mg, 0.15 mmol) were added to the mixture, which was stirred at 80 C for 5 h in an oil bath until substrate disappeared as judged by TLC. The reaction mixture was allowed to cool to rt, DME was evaporated, and water (40.0 ml) and ether (20.0mL) were added. The layers were separated and the aqueous layer was extracted with diethylether (3 20.0 ml). The combined organic layers were washed with brine, dried over magnesium sulfate, filtered, and evaporated in vacuo to obtain a yellow oil, which was purified further using column chromatography on silica gel (eluent: heptane 30% EtAc in heptane). The title compound ii was isolated as a white 7

amorphous solid (1.92g, 85%) [4].The experimental procedures from ii to 5 were according to the above A(a). The mixture of 5 (87.9 mg, 0.2 mmol, 1 equiv), 4-methyl iodobenzene 2b (174.4 mg, 0.8 mmol, 4.0 equiv), Cs 2 C 3 (325.8 mg, 1 mmol, 5 equiv),tbai (36.9 mg, 0.1 mmol, 0.5 equiv) in DMS (2 ml) was stirred under nitrogen atmosphere at 120 C for 12 h. After the completion of the reaction (monitored by TLC), the reaction mixture was filtered and the filtrate was washed by H 2 and saturated salt solution and then evaporated under reduced pressure, the crude product was purified by column chromatography (petroleum ether : ethyl acetate = 10:1) to provide a pair of isomers of 7 and 7 in a 1: 2 ratio 3aa as a white solid (40 mg, 42%). The mixture of 1a (217.9 mg, 0.6 mmol, 1 equiv), 2-(trimethylsilyl)phenyltrifluoromethanesulfonate 2a (268.5 mg, 0.9 mmol, 1.5 equiv), CsF (182.4 mg, 1.2 mmol, 2 equiv), Cs 2 C 3 (293.2 mg, 0.9 mmol, 1.5 equiv) in PhMe/MeC (1:1) (6 ml) was stirred at 80 C for 6 h. The reaction mixture was cooled to room temperature. nce cooled, the reaction was passed through a plug of silica gel using EtAc. The crude product was purified by column chromatography (petroleum ether : ethyl acetate = 10:1) to provide the raw material 6 as white solid (158.8 mg, 85%). 8

The mixture of 6 (62.3 mg, 0.2 mmol, 1 equiv), iodobenzene 2a (163.2 mg, 0.8 mmol, 4.0 equiv), Cs 2 C 3 (325.8 mg, 1 mmol, 5 equiv),tbai (36.9 mg, 0.1 mmol, 0.5 equiv) in DMS (2 ml) was stirred under nitrogen atmosphere at 120 C for 12 h. o desired product 3aa was observed. The recovery rate of raw material 6 was 96%. 9

(D) Analytical Data 1-methyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3aa): white solid, isolated yield 65% (50 mg); mp: 179.5-179.9 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.91 (d, J = 8.0 Hz, 1H), 7.83 (d, J =8.0 Hz, 1H), 7.45 (d, J = 7.5 Hz, 1H), 7.42-7.37 (m, 3H), 7.24-7.14 (m, 3H), 7.06-7.03 (m, 2H), 6.76 (t, J = 7.5 Hz, 1H), 6.70 (t, J=7.5 Hz, 1H), 6.62 (d, J = 7.5 Hz, 1H), 6.40 (d, J = 7.5 Hz, 1H), 5.84 (d, J=7.5 Hz,1H), 3.63 (d, J = 14.5 Hz, 1H) 2.57(s, 3H), 2.52(d, J=15.0Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.9, 142.2, 142.0, 140.8, 135.9, 135.0, 134.2, 133.4, 133.0, 131.5, 130.4, 129.1, 128.7, 128.2, 128.0, 127.9, 127.8, 127.1, 125.9, 124.6, 124.0, 123.6, 122.1, 108.3, 52.6, 41.1, 26.0. HRMS (ESI) m/z calcd for C 28 H 22 + (M+H) + 388.1696, found 388.1699. 1-ethyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3ba): white solid, isolated yield 61% (49 mg); mp: 114.3-115.9 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.91 (d, J = 7.5 Hz, 1H), 7.84 (d, J = 7.5 Hz, 1H), 7.42-7.36 (m, 4H), 7.24 (t, J = 2.0 Hz, 1H), 7.20-7.14 (m, 2H), 7.05 (d, J = 6.5 Hz, 2H), 6.75-6.69 (m, 2H), 10

6.65 (d, J=7.5 Hz, 1H), 6.41 (d, J=7.0 Hz, 1H), 5.84 (d, J = 6.5 Hz, 1H), 3.64 (d, J = 14.5 Hz, 1H), 3.34-3.29 (m, 1H), 2.79-2.75 (m, 1H), 2.51 (d, J=14.5 Hz, 1H), 1.00 (t, J=7.0 Hz, 3H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.4, 142.2, 141.0, 140.8, 135.9, 135.0, 134.1, 133.5, 133.0, 131.5, 130.3, 129.0, 128.6, 128.0, 127.9, 127.8, 127.7, 127.0, 125.9, 124.5, 123.9, 123.7, 121.8, 108.3, 52.4, 41.3, 34.4, 12.7. HRMS (ESI) m/z calcd for C 29 H 24 + (M+H) + 402.1852, found 402.1856. 1-benzyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3ca): white solid, isolated yield 81% (75 mg); mp: 221.6-222.8 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.93 (d, J = 8.0 Hz, 1H), 7.85 (d, J = 7.5 Hz, 1H), 7.49 (d, J = 7.5 Hz, 1H), 7.43 (t, J = 7.5 Hz, 3H), 7.29-7.26 (m, 2H), 7.25-7.20 (m, 3H) 7.17 (d, J = 7.5 Hz, 2H), 7.09-7.06 (m, 3H), 6.83 (t, J = 7.5 Hz, 1H), 6.68 (t, J = 7.5 Hz, 1H), 6.52 (d, J = 8.0 Hz, 1H), 6.41 (d, J = 7.5 Hz,1H), 5.89 (d, J = 7.0 Hz, 1H), 4.71 (d, J = 16.0 Hz, 1H), 3.73 (d, J = 14.5 Hz, 1H), 3.47 (d, J = 15.5 Hz, 1 H), 2.60 (d, J=15.0 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 177.8, 141.0, 139.8, 139.5, 135.1, 134.6, 133.8, 133.0, 132.2, 131.6, 130.2, 129.4, 128.0, 127.5, 126.8, 126.6, 126.2, 126.0, 125.9, 124.7, 123.3, 122.8, 122.5, 120.9, 108.0, 51.3, 42.0, 40.1. HRMS (ESI) m/z calcd for C 34 H 26 + (M+H) + 464.2009, found 464.2004. 11

F 1-(4-fluorobenzyl)-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3da): white solid, isolated yield 71% (68 mg); mp: 235.3-235.4 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ:7.93 (dd, J = 7.5 Hz, 1.0 Hz, 1H), 7.85 (d, J = 7.5 Hz, 1H), 7.48 (d, J = 7.5 Hz, 1H), 7.44-7.41 (m, 3H), 7.26-7.22 (m, 2H), 7.15 (dd, J = 8.5 Hz, 5.5 Hz, 2H), 7.11-7.06 (m, 3H ), 6.96 (td, J=11.5 Hz, 2.5 Hz, 2H), 6.82 (t, J=7.5 Hz, 1H), 6.69 (t, J = 7.0 Hz, 1H), 6.51 (d, J = 7.5 Hz, 1H), 6.41 (d, J=7.0 Hz, 1H), 5.88 (d, J=8.0 Hz, 1H), 4.63 (d, J=16.0 Hz, 1H), 3.72 (d, J=14.5 Hz, 1H), 3.46 (d, J=15.5 Hz, 1H), 2.55 (d, J=14.5 Hz, 1H), ; 13 CMR (125 MHz, CDCl 3 ) δ: 179.0, 162.1 (d, J = 244.3 Hz), 142.1, 140.7 (d, J = 3.8 Hz), 135.8, 134.9, 134.0, 133.4, 132.7, 132.0 (d, J = 3.3 Hz), 131.4, 130.6, 129.1, 128.8 (d, J = 8.1 Hz), 128.6, 128.0, 127.9, 127.8, 127.2, 125.9, 124.5, 124.0, 123.8, 122.2, 115.5 (d, J = 21.5 Hz), 109.0, 52.5, 42.6, 41.3. HRMS (ESI) m/z calcd for C 34 H 25 F + (M+H) + 482.1915, found 482.1913. 1-(4-methylbenzyl)-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3ea): white solid, isolated yield 65% (62 mg); mp: 178.9-180.1 o C(uncorrected); 1 H 12

MR(500 MHz, CDCl 3 ) δ: 7.92 (d, J = 7.5 Hz, 1H), 7.84 (d, J=8.0 Hz, 1H), 7.49 (d, J = 7.5 Hz, 1H), 7.41 (t, J = 7.5 Hz, 3H), 7.24-7.21 (m, 2H), 7.09-7.05 (m, 7H), 6.82 (t, J = 7.0 Hz, 1H), 6.65 (t, J = 7.5 Hz, 1H), 6.53 (d, J = 8.0 Hz, 1H), 6.39 (d, J = 7.0 Hz, 1H), 5.88 (d, J = 7.0 Hz, 1H), 4.67 (d, J = 16.0 Hz, 1H), 3.72 (d, J = 14.5 Hz, 1H), 3.43 (d, J =15.5 Hz, 1 H), 2.57 (d, J = 14.5 Hz, 1H), 2.28 (s, 3H); 13 CMR(125 MHz, CDCl 3 ) δ: 178.9, 142.1, 141.0, 140.7, 137.0, 135.7, 135.0, 134.1, 133.3, 133.2, 132.8, 131.3, 130.5, 129.3, 129.1, 128.6, 128.0, 127.9, 127.8, 127.1, 125.8, 124.4, 124.0, 123.6, 121.9, 109.1, 52.4, 42.9, 41.2, 21.1. HRMS (ESI) m/z calcd for C 35 H 28 + (M+H) + 478.2165, found 478.2166. 1-benzyl-5-methyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3fa): white solid, isolated yield 83% (79 mg); mp: 197.4-198.4 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.94 (d, J = 7.0 Hz, 1H), 7.85 (d, J = 7.0 Hz, 1H), 7.47 (s, 1H), 7.42 (s, 3H), 7.26-7.20 (m, 5H), 7.15 (d, J = 6.0 Hz, 2H), 7.08 (s, 2H), 6.86 (t, J = 8.0 Hz, 2H), 6.40 (d, J = 7.0 Hz, 1H), 6.21 (s, 1H), 5,92 (d, J = 6.0 Hz, 1H), 4.68 (d, J = 15.5 Hz, 1H), 3.72 (d, J = 9.5 Hz, 1H), 3.45 (d, J = 16.0 Hz, 1H), 2.61 (d, J = 14.5 Hz, 1H), 2.01 (s, 3H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.9, 142.2, 140.7, 138.6, 136.4, 135.8, 134.9, 134.3, 133.5, 132.9, 131.5, 131.4, 130.5, 129.2, 128.7, 128.6, 128.3, 127.9, 127.8, 127.3, 127.1, 125.9, 124.5, 124.4, 123.9, 108.9, 52.5, 43.2, 41.3, 20.9. HRMS (ESI) m/z calcd for C 35 H 28 + (M+H) + 478.2165, found 478.2168. 13

1-benzyl-6-methyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3ga): white solid, isolated yield 80% (76 mg); mp: 203.1-203.6 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.92 (d, J = 7.5 Hz, 1H),7.85 (d, J = 7.5 Hz, 1H), 7.48 (d, J = 6.5 Hz, 1H), 7.42 (d, J =7.0 Hz, 3H), 7.28-7.22 (m, 5H), 7.16 (d, J = 7.0 Hz, 2H), 7.08 (t, J = 8.0 Hz, 2H), 6.84 (t, J = 7.5 Hz, 1H), 6.48 (d, J = 7.0 Hz, 1H), 6.35 (s, 1H), 6.27 (d, J = 7.0 Hz, 1H), 5.93 (d, J = 7.0 Hz, 1H), 4.64 (d, J = 15.5 Hz, 1H), 3.71 (d, J = 15.0 Hz, 1H), 3.48 (d, J = 16.0 Hz, 1H), 2.57 (d, J = 14.5 Hz, 1H), 2.22 (s, 3H); 13 CMR (125 MHz, CDCl 3 ) δ: 179.3, 142.2, 141.1, 140.9, 138.1, 136.5, 135.8, 135.1, 134.4, 133.0, 131.4, 130.6, 129.2, 128.7, 128.0, 127.8, 127.7, 127.3, 127.1, 125.9, 124.5, 124.0, 123.4, 122.6, 110.0, 52.3, 43.2, 41.5, 21.8. HRMS (ESI) m/z calcd for C 35 H 28 + (M+H) + 478.2165, found 478.2167. 1-benzyl-6-methoxy-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3ha): white solid, isolated yield 73% (72 mg); mp: 185.3-186.6 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.92 (d, J = 7.5 Hz, 1H), 7.84 (d, J = 7.5 Hz, 1H), 7.48 (d, J = 7.5 Hz, 1H), 7.42 (dd, J = 13.0 Hz, 6.0 Hz, 3H), 7.29-7.19 (m, 5H), 7.16 (d, J = 7.5 14

Hz, 2H), 7.08 (t, J = 7.0 Hz, 2H), 6.90 (t, J = 7.5 Hz, 1H), 6.29 (d, J = 8.0 Hz, 1H), 6.17 (dd, J = 8.0 Hz, 1.5 Hz, 1H), 6.13 (s, 1H), 5.99 (d, J = 7.0 Hz, 1H), 4.66 (d, J = 16 Hz, 1H), 3.70 (d, J = 9.5 Hz, 1H), 3.65 (s, 3H), 3,43 (d, J = 15.5 Hz, 1H), 2.56 (d, J = 14.5 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 179.5, 160.0, 142.2, 142.0, 140.8, 136.2, 135.7, 135.0, 134.4, 133.0, 131.4, 130.5, 129.1, 128.6, 128.0, 127.7, 127.4, 127.1, 125.9, 125.6, 124.5, 124.1, 123.9, 105.4, 97.3, 55.3, 52.0, 43.2, 41.5. HRMS (ESI) m/z calcd for C 35 H 28 + 2 (M+H) + 494.2115, found 494.2118. 1-benzyl-5-chloro-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3ia): yellow solid, isolated yield 69% (69 mg); mp: 219.4-221.4 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ:7.94 (d, J = 8.0 Hz, 1H), 7.84 (d, J = 7.5 Hz, 1H), 7.48-7.40 (m, 4H), 7.29-7.20 (m, 5H), 7.13 (d, J = 7.0 Hz, 2H), 7.09 (t, J = 7.0 Hz, 2H), 7.03 (d, J = 2.0 Hz, 1H), 6.85 (t, J = 7.0 Hz, 1H), 6.42 (d, J = 8.0 Hz, 1H), 6.37 (s, 1H), 5.98 (d, J = 7.0 Hz, 1H), 4.72 (d, J = 15.5 Hz, 1H), 3.72 (d, J = 14.5 Hz, 1H), 3.44 (d, J = 15.5 Hz, 1H), 2.58 (d, J = 15.0 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.6, 142.2, 140.5, 139.6, 135.7, 134.9, 134.6, 133.3, 132.1, 131.4, 130.6, 129.0, 128.7, 128.6, 128.1 (double), 128.0 (double), 127.5, 127.3 (double), 127.0, 125.9, 124.6, 124.1, 124.0, 110.0, 52.6, 43.3, 41.2.HRMS (ESI) m/z calcd for C 34 H 25 Cl + (M+H) + 498.1619, found 498.1618. 15

1-benzyl-6-chloro-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3ja): white solid, isolated yield 70% (70 mg); mp: 219.4-221.4 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.93 (d, J = 7.5 Hz, 1H), 7.84 (d, J = 7.5 Hz, 1H), 7.47-7.43 (m, 4H), 730-7.24 (m, 5H), 7.15 (d, J = 6.5 Hz, 2H), 7.08 (dd, J = 18.0 Hz, 7.0 Hz, 2H), 6.90 (t, J = 7.0 Hz, 1H), 6.65 (d, J = 7.5 Hz, 1H), 6.52 (s, 1H), 6.30 (d, J = 8.0 Hz, 1H), 5.97 (d, J = 6.5 Hz, 1H), 4.68 (d, J = 15.5 Hz, 1H), 3.71 (d, J = 14.5 Hz, 1H), 3.43 (d, J = 15.5 Hz, 1H), 2.54 (d, J = 15.0 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 179.0, 142.2, 142.1, 140.6, 135.7, 134.8, 133.8, 133.6, 132.4, 131.7, 131.4, 130.6, 128.9, 128.8, 128.6, 128.1, 128.0, 127.9, 127.6, 127.3, 127.0, 126.0, 124.6, 124.5, 124.0, 121.9, 109.6, 52.1, 43.3, 41.3. HRMS (ESI) m/z calcd for C 34 H 25 Cl + (M+H) + 498.1619, found 498.1617. 1-benzyl-5-fluoro-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3ka): white solid, isolated yield 68% (65 mg); mp: 189.3-190.4 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.94 (d, J = 7.5 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.49-7.47 (m, 1H), 7.45-7.41 (m, 3H),7.30-7.21 (m, 5H), 7.15 (d, J = 7.0 Hz, 2H), 7.10-7.08 (m, 16

2H), 6.85 (t, J = 7.5 Hz, 1H), 6.78 (td, J = 9.0 Hz, 2.5 Hz, 1H), 6.42 (dd, J = 8.5 Hz, 4.0 Hz, 1H), 6.16 (dd, J = 8.0 Hz, 2.5 Hz, 1H), 5.95 (d, J = 7.5 Hz, 1H), 4.72 (d, J = 16.0 Hz, 1H), 3.74 (d, J = 14.5 Hz, 1H), 3.42 (d, J = 16.0 Hz, 1H), 2.58 (d, J = 15.0 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.7, 158.6 (d, J = 239.3 Hz), 142.2, 140.6, 137.0, 136.0, 135.9, 135.7, 134.8 (d, J = 8.1 Hz), 134.7, 133.5, 132.2, 131.4, 130.6, 129.1, 128.7, 128.6, 128.1, 128.0, 127.5, 127.3, 127.1, 126.0, 124.3 (d, J = 66.0 Hz), 114.3 (d, J = 23.3 Hz), 111.8 (d, J = 24.5 Hz), 109.5 (d, J = 8.0 Hz), 52.7, 43.3, 41.2.HRMS (ESI) m/z calcd for C 34 H 25 F + (M+H) + 482.1915, found 482.1914. 1-benzyl-8'-phenyl-5-(trifluoromethyl)-10'H-spiro[indoline-3,9'-phenanthren]-2- one (3la): white solid, isolated yield 65% (69 mg); mp: 80.5-81.5 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.95 (d, J = 7.5 Hz, 1H), 7.85 (d, J = 7.5 Hz, 1H), 7.45 (d, J = 6.5 Hz, 3H), 7.40 (t, J = 7.5 Hz, 1H), 7.35 (d, J = 7.5 Hz, 1H), 7.30-7.22 (m, 5H), 7.16 (d, J = 7.0 Hz, 2H), 7.11 (d, J = 7.0 Hz, 1H), 7.06 (d, J = 7.0 Hz, 1H), 6.84 (t, J = 7.0 Hz, 1H), 6.60 6.57 (m, 2H), 5.94 (d, J = 6.5 Hz, 1H), 4.75 (d, J = 16.0 Hz, 1H), 3.71 (d, J = 14.5 Hz, 1H), 3.53 (d, J = 15.5 Hz, 1H), 2.58 (d, J = 15.5 Hz, 1 H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.8, 143.9, 142.1, 140.6, 135.9, 135.5, 134.7, 133.7, 133.2, 131.9, 131.4, 130.5, 128.9, 128.8, 128.6, 128.2, 128.1 (q, J = 4.9 Hz), 127.7, 127.4, 127.1, 126.0, 125.7, 124.2, 124.2 (q, J = 32.3 Hz), 124.0 (q, J = 269.5 Hz), 120.5 (q, J = 3.6 Hz), 108.8, 52.3, 43.4, 41.3. HRMS (ESI) m/z calcd for 17

C 35 H 25 F 3 + (M+H) + 532.1883, found 532.1885. 1-benzyl-2-oxo-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthrene]-5-carbonitrile( 3ma): white solid, isolated yield 38% (37 mg); mp: 198.3-198.9 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.97 (d, J = 8.0 Hz, 1H), 7.87 (d, J = 7.5 Hz, 1H), 7.49-7.45 (m, 3H), 7.42-7.40 (m, 2H), 7.31-7.29 (m, 3H), 7.27 (s, 1H), 7.25 (s, 2H), 7.14 (d, J = 7.0 Hz, 2H), 7.09 (dd, J = 15.5 Hz, 7.5 Hz, 2H), 6.84 (t, J = 7.0 Hz, 1H), 6.64 (s, 1H), 6.57 (d, J = 8.0 Hz, 1H), 5.91 (d, J = 6.5 Hz, 1H), 4.75 (d, J = 16.0 Hz, 1H), 3.72 (d, J = 15.0 Hz, 1H), 3.48 (d, J = 16.0 Hz, 1H), 2.55 (d, J = 14.5 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.9, 145.0, 142.1, 140.4, 135.7, 135,2, 134.5, 134.2, 133.3, 132.7,131.6, 131.4, 130.7, 128.9, 128.9, 128.5, 128.4, 128.3, 128.2, 127.8, 127.5, 127.0, 126.9, 126.0, 124.8, 124.3, 119.1, 109.5, 105.1, 52.1, 43.5, 41.1. HRMS (ESI) m/z calcd for C 35 H 25 2 + (M+H) + 489.1961, found 489.1956. 1-benzyl-6'-fluoro-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3na) : yellow solid, isolated yield 79% (76 mg); mp: > 250 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ:7.79 (d, J = 7.5 Hz, 1H), 7.63 (d, J = 9.5 Hz, 1H), 7.48-7.43 (m, 3H), 18

7.30-7.27 (m, 4H), 7.23 (d, J = 7.0 Hz, 1H), 7.16 (d, J = 7.5 Hz, 2H), 7.10-7.07 (m, 2H), 6.85-6.81 (m, 2H), 6.69 (t, J = 7.5 Hz, 1H), 6.52 (d, J = 7.5 Hz, 1H), 6.38 (d, J = 7.5 Hz, 1H), 5.87 (d, J = 7.5 Hz, 1H), 4.69 (d, J = 16.0 Hz, 1H), 3.71 (d, J = 14.5 Hz, 1H), 3.46 (d, J = 16.0 Hz, 1H), 2.59 (d, J = 14.5 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.8, 162.9 (d, J = 245.4 Hz), 144.3 (d, J = 7.9 Hz), 140.9, 139.7, 138.0 (d, J = 7.8 Hz), 136.1, 134.1, 133.2, 132.9, 130.3, 128.8, 128.7(double), 128.4, 128.1 (d, J =4.3 Hz), 128.0, 127.6, 127.4, 127.1, 126.0, 124.6, 123.5, 122.1, 117.9 (d,j= 21.3 Hz), 110.6 (d, J = 21.9 Hz), 109.2, 52.0, 43.2, 41.3.HRMS (ESI) m/z calcd for C 34 H 25 F + (M+H) + 482.1915, found 482.1916. 1-benzyl-6'-methoxy-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3oa): white solid, isolated yield 63% (62 mg); mp: 141.6-141.9 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.83 (d, J = 7.0 Hz, 1H), 7.50-7.48 (m, 2H), 7.44-7.43(m, 2H), 7.27-7.21(m, 6H), 7.16 (d, J = 7.0 Hz, 2H), 7.08-7.05 (m, 2H), 6.83 (t, J = 7.0 Hz, 1H), 6.69-6.65 (m, 2H), 6.51 (d, J = 8.0 Hz, 1H), 6.39 (d, J = 7.0 Hz, 1H), 5.90 (d, J = 7.0 Hz, 1H), 4.70 (d, J = 16 Hz, 1H), 3.86 (s, 3H), 3.70 (d, J = 14.5 Hz, 1H), 3.46 (d, J = 15.5 Hz, 1H), 2.58 (d, J = 14.5 Hz, 1H), ; 13 CMR (125 MHz, CDCl 3 ) δ: 179.2, 158.8, 143.4, 140.9, 140.7, 137.1, 136.3, 134.9, 133.7, 133.1, 130.4, 129.0, 128.6, 128.0, 127.9, 127.8, 127.3, 127.2, 127.1, 126.7, 125.9, 124.5, 123.6, 122.0, 116.3, 110.0, 109.1, 55.4, 52.0, 43.2, 41.5. HRMS (ESI) m/z calcd for C 35 H 28 + (M+H) + 19

494.2115, found 494.2118. 1-benzyl-8'-fluoro-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3pa) : white solid, isolated yield 87% (71 mg); mp: 201.7-202.3 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.84 (d, J = 7.5 Hz, 1H), 7.73 (d, J = 7.5 Hz, 1H), 7.44-7.41 (t,j = 7,0 Hz, 3H), 7.38-7.33 (m, 3H), 7.31-7.23 (m, 2H), 7.14 (d, J = 7.5 Hz, 1H), 7.06 (t, J = 7.5 Hz, 1H), 6.94 (t, J = 9.0 Hz, 1H), 6.75 (d, J = 7.5 Hz, 1H), 6.64 (t, J = 7.0 Hz, 1H), 6.35 (d, J = 7.0 Hz, 1H), 5.14 (d, J = 15.5 Hz, 1H), 5.02 (d, J = 16.0 Hz, 1H), 3.80 (d, J = 15.0 Hz, 1H), 2.78 (d, J = 15.0 Hz); 13 CMR (125 MHz, CDCl 3 ) δ:179.3, 159.4 (d, J = 245.8 Hz), 141.3, 136.7 (d, J = 4.0 Hz), 135.9, 133.1, 132.6, 130.9, 129.3 (d, J = 20.5 Hz), 129.2, 128.7, 128.4, 128.3, 127.8, 127.6, 127.4 (d, J = 1.3 Hz), 124.2, 124.0 (d, J = 14.6 Hz), 123.3, 122.3, 120.0, 115.3 (d, J = 22.5 Hz), 109.4, 48.9, 44.2, 39.5. HRMS (ESI) m/z calcd for C 28 H 21 F + (M+H) + 406.1602, found 406.1604. 1-benzyl-2'-methyl-8'-(p-tolyl)-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3cb): white solid, isolated yield 67% (66 mg); mp: 176.8-178.1 o C (uncorrected); 1 H 20

MR (500 MHz, CDCl 3 ) δ: 7.88 (d, J = 7.5 Hz, 1H), 7.72 (d, J = 7.5 Hz, 1H), 7.38 (t, J = 7.5 Hz, 2H), 7.28-7.17 (m, 7H), 7.08-7.04(m, 2H), 6.89 (s, 1H), 6.68-6.63 (m, 2H), 6.52 (d, J = 8.0 Hz, 1H), 6.43 (d, J = 7.0 Hz, 1H), 5.77 (d, J = 7.5 Hz, 1H), 4.73 (d, J = 16.0 Hz, 1H), 3.71 (d, J = 15.0 Hz, 1H), 3.44 (d, J = 15.5 Hz, 1H), 2.54 (d, J = 15.5 Hz, 1H), 2.36 (s, 3H), 2.30 (s, 3H); 13 CMR (125 MHz, CDCl 3 ) δ:179.1, 142.0, 140.9, 137.9, 137.6, 136.5, 136.2, 135.7, 134.0, 133.5, 132.6, 132.2, 131.0, 130.4, 129.3, 128.9, 128.7, 128.6, 128.5, 127.9, 127.6, 127.3, 127.0, 126.3, 124.3, 123.7, 123.5, 122.0, 109.1, 52.5, 43.1, 41.2, 21.1. HRMS (ESI) m/z calcd for C 36 H 30 + (M+H) + 492.2322, found 492.2322. 1-benzyl-2'-methoxy-8'-(4-methoxyphenyl)-10'H-spiro[indoline-3,9'-phenanthren ]-2-one (3cc): white solid, isolated yield 65% (68 mg); mp: 193.2-194.1 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.84 (dd, J = 7.5 Hz, 0.5 Hz, 1H), 7.76 (d, J = 6.0 Hz, 1H), 7.40-7.36 (m, 2H), 7.29 (t, J = 7.0 Hz, 2H), 7.24-7.19 (m, 3H), 7.08 (td, J = 8.0 Hz, 1.0 Hz, 1H), 7.01 (dd, J = 7.5 Hz, 1.0 Hz, 1H), 6.96 (td, J = 6.0 Hz, 2.5 Hz, 2H), 6.69 (t, J = 7.5 Hz, 1H), 6.62 (d, J = 2.5 Hz, 1H), 6.55 (d, J = 8.0 Hz, 1H), 6.46 (d, J = 7.0 Hz, 1H), 6.36 (dd, J = 8.5 Hz, 3 Hz, 1H), 5.79 (dd, J = 7.0 Hz, 2.0 Hz, 1H), 4.80 (d, J = 15.5 Hz, 1H), 3.83 (s, 3H), 3.78 (s, 3H), 3.71 (d, J = 9.5 Hz, 1H), 3.56 (d, J = 16.0 Hz, 1H), 2.52 (d, J = 14.5 Hz, 1H) ; 13 CMR (125 MHz, 21

CDCl 3 ) δ: 179.2, 159.3, 158.6, 141.7, 140.9, 136.3, 135.7, 134.4, 133.7, 133.5, 133.4, 131.8, 130.7, 130.3, 128.6, 127.9, 127.7, 127.4, 127.2, 125.8, 123.8, 123.2, 122.1, 113.6, 113.1, 111.5, 109.0, 55.4, 55.2, 52.5, 43.3, 41.6. HRMS (ESI) m/z calcd for C 36 H 30 + 3 (M+H) + 524.2220, found 524.2219. 1-benzyl-2'-(dimethylamino)-8'-(4-(dimethylamino)phenyl)-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3cd): yellow solid, isolated yield 52% (57 mg); mp: 113.0-113.5 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.78 (d, J = 7.5 Hz, 1H), 7.71 (d, J = 9.0 Hz, 1H) 7.33 (t, J = 7.5 Hz, 2H), 7.30-7.27 (m, 2H), 7.24-7.19 (m, 3H), 7.07 (td, J = 7.5 Hz, 4.5 Hz, 1H), 6.98 (d, J = 7.5 Hz, 1H), 6.83 (dd, J = 8.5 Hz, 1.5 Hz, 1H), 6.76 (dd, J = 8.5 Hz, 1.5 Hz, 1H), 6.69 (t, J = 7.5 Hz, 1H), 6.54 (t, J = 8.0 Hz, 2H), 6.40 (s, 1H), 6.17 (d, J = 7.0 Hz, 1H), 5.75 (dd, J = 8.5 Hz, 1.5 Hz, 1H), 4.81 (d, J = 16.0 Hz, 1H), 3.71 (d, J = 14.5 Hz, 1H), 3.55 (d, J = 16.0 Hz, 1H), 2.97 (s, 6H), 2.94 (s, 6H), 2.48 (d, J = 14.5 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ:179.5, 150.0, 149.6, 142.1, 141.1, 136.6, 136.2, 134.0, 133.9, 133.4, 131.3, 129.9, 129.8, 128.6, 127.6, 127.5, 127.3, 127.2, 125.3, 123.9, 122.3, 122.0, 112.5, 112.1, 111.5, 109.8, 108.8, 52.6, 43.5, 41.9, 40.8, 40.3. HRMS (ESI) m/z calcd for C 38 H 36 3 + (M+H) + 550.2853, found 550.2854. 22

1-benzyl-2'-fluoro-8'-(4-fluorophenyl)-10'H-spiro[indoline-3,9'-phenanthren]-2-o ne (3ce): white solid, isolated yield 59% (59 mg); mp: 190.2-191.4 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.88 (d, J = 7.0 Hz, 1H), 7.80 (d, J = 5.0 Hz, 1H), 7.43-7.40 (m, 2H), 7.28 (d, J = 6.5 Hz, 2H), 7.25 (s, 1H), 7.19 (d, J = 6.0 Hz, 2H) 7.10 (s, 3H), 7.04 (d, J = 7.0 Hz, 1H), 6.81 (d, J = 7.5 Hz, 1H), 6.73 (t, J = 7.5 Hz, 1H), 6.57 (d, J = 7.5 Hz, 1H), 6.53 (t, J = 8.0 Hz, 1H), 6.43 (d, J = 7.0 Hz, 1H), 5.84 (s, 1H), 4.81 (d, J = 15.5 Hz, 1H), 3.69 (d, J = 14.5 Hz, 1H), 3.59 (d, J = 15.5 Hz, 1H), 2.56 (d, J = 14.5 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.8, 162.4 (d, J = 246.5 Hz), 162.0 (d, J = 245.1 Hz), 141.2, 140.8, 136.5, 135.5 (d, J = 98.2 Hz), 133.9, 133.0, 132.5 (d, J = 8.0 Hz), 131.3, 131.0, 130.8 (d, J = 8.1 Hz), 128.7, 128.3, 127.9, 127.5, 127.2, 126.3 (d, J = 8.2 Hz), 123.9, 123.6, 122.3, 115.6 (d, J = 21.6 Hz), 115.9 (d, J = 46.8 Hz), 114.9 (d, J = 4.3 Hz), 112.5 (d, J = 20.9 Hz), 109,3, 52.3, 43.2, 41.2. HRMS (ESI) m/z calcd for C 34 H 24 F 2 + (M+H) + 500.1821, found 500.1824. 1-benzyl-2'-chloro-8'-(4-chlorophenyl)-10'H-spiro[indoline-3,9'-phenanthren]-2-23

one (3cf): white solid, isolated yield 66% (70 mg); mp: 198.4-198.6 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.90 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.5 Hz, 1H), 7.45-7.39 (m, 4H), 7.32-7.29 (m, 2H), 7.26-7.23 (m, 2H), 7.19 (d, J = 7.0 Hz, 2H), 7.13-7.10 (m, 2H), 7.07 (d, J = 7.5 Hz, 1H), 6.80 (d, J = 8.0 Hz, 1H), 6.73 (t, J = 7.5 Hz, 1H), 6.57 (d, J = 8.0 Hz, 1H), 6.43 (d, J = 7.0 Hz, 1H), 5.79(d, J = 8.0 Hz, 1H), 4.79 (d, J = 15.5 Hz, 1H), 3.68 (d, J = 14.5 Hz, 1H), 3.55 (d, J = 15.5 Hz, 1H), 2.57 (d, J = 15.0 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.7, 141.0, 140.8, 138.9, 135.8, 135.0, 134.5, 134.1, 133.7, 133.3, 132.9, 132.1, 131.4, 130.5, 128.7, 128.6, 128.4, 128.2, 128.0, 127.5, 127.1, 125.9, 125.8, 124.2, 123.7, 122.4, 109.5, 52.3, 43.2, 40.9. HRMS (ESI) m/z calcd for C 34 H 24 Cl 2 + (M+H) + 532.1230, found 532.1229. F 3 C CF 3 1-benzyl-2'-(trifluoromethyl)-8'-(4-(trifluoromethyl)phenyl)-10'H-spiro[indoline- 3,9'-phenanthren]-2-one(3cg): white solid, isolated yield 61% (73 mg); mp: 186.1-186.4 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.99 (dd, J = 16 Hz, 7.5 Hz, 2H), 7.70 (d, J = 8.0 Hz, 2H), 7.61 (d, J = 7.5 Hz, 1H), 7.50 (t, J = 7.5 Hz, 1H), 7.38 (s, 1H), 7.31-7.28 (m, 2H), 7.25-7.22 (m, 1H), 7.16-7.13 (m, 5H), 6.73 (t, J = 7.5 Hz, 1H), 6.56 (d, J = 8.0 Hz, 1H), 6.40 (d, J = 7.5 Hz, 1H), 6.01 (d, J = 7.5 Hz, 1H), 4.71 (d, J = 15.5 Hz, 1H), 3.73 (d, J = 15.0 Hz, 1H), 3.44 (d, J = 15.5 Hz, 1H), 2.70 (d, J = 15.0 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.4, 143.9, 140.9, 140.7, 24

138.0, 135.6, 134.7, 134.3, 133.4, 132.6, 131.9, 131.1, 130.7, 129.8 (q, J = 32.2 Hz), 129.6, 128.8, 128.6, 128.3, 127.6, 127.0,125.5, 125.0, 124.8 (q, J = 6.0 Hz), 124.2 (q, J = 270.6 Hz), 124.0 (q, J = 270.1 Hz), 123.6, 122.8 (q, J = 3.5 Hz), 122.5, 109.6, 52.2, 43.1, 40.9. HRMS (ESI) m/z calcd for C 36 H 24 F 6 + (M+H) + 600.1757, found 600.1757. 8'-([1,1'-biphenyl]-4-yl)-1-benzyl-2'-phenyl-10'H-spiro[indoline-3,9'-phenanthren ]-2-one (3ch): white solid, isolated yield 67% (83 mg); mp: 216.8-218.5 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.98 (d, J = 7.5 Hz, 1H), 7.92 (d, J = 8.5 Hz, 1H), 7.68-7.66 (m, 2H), 7.63-7.57 (m, 5H), 7.50-7.43 (m, 3H), 7.40-7.37 (m, 3H), 7.35 (s, 1H), 7.30 (t, J = 7.5 Hz, 1H), 7.26-7.23 (m, 2H), 7.19-7.17 (m, 1H), 7.14 (d, J = 7.5 Hz, 1H), 7.11 (d, J = 7.5 Hz, 2H), 7.09-7.04 (m, 2H), 6.69 (t, J = 7.5 Hz, 1H), 6.52-6.50 (m, 2H), 5.97 (dd, J = 7.5 Hz, 1.0 Hz, 1H), 4.78 (d, J = 15.5 Hz, 1H), 3.82 (d, J = 14.5 Hz, 1H), 3.43 (d, J = 15.5 Hz, 1H), 2.69 (d, J = 15.0 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 179.1, 141.8, 140.9, 140.4, 140.2, 139.9, 139.7, 136.1, 135.5, 134.3, 133.9, 133.4, 133.2, 131.2, 131.1, 129.7, 128.9, 128.7, 128.6, 128.1, 127.9, 127.4, 127.3, 127.2, 127.0 (double), 126.9, 126.8, 126.7, 126.4, 124.9, 124.5, 124.0, 123.8, 122.2, 109.2, 52,5, 43.2, 41.4. HRMS (ESI) m/z calcd for C 46 H 34 + (M+H) + 616.2635, found 616.2632. 25

1-benzyl-8'-(4-(methoxycarbonyl)phenyl)-2-oxo-10'H-spiro[indoline-3,9'-phenant hrene]-2'-carboxylate (3ci): yellow solid, isolated yield 36% (42 mg); mp: 242.3-242.7 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 8.10 (dd, J = 15.5 Hz, 8.0 Hz, 2H), 8.01 (d, J = 7.5 Hz, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.77 (s, 1H), 7.55 (t, J = 8.0 Hz, 2H), 7.49 (t, J = 7.5 Hz, 1H), 7.31-7.22 (m, 3H), 7.16 (m, 4H), 6.69 (t, J = 7.5 Hz, 1H), 6.57 (d, J = 7.5 Hz, 1H), 6.37 (d, J = 7.0 Hz, 1H), 5.98 (d, J = 7.5 Hz, 1H), 4.66 (d, J = 15.5 Hz, 1H), 3.97 (s, 3H), 3.90 (s, 3H), 3.72 (d, J = 15.0 Hz, 1H), 3.45 (d, J = 15.5 Hz, 1H), 2.69 (d, J = 14.5 Hz, 1H) ; 13 CMR (125 MHz, CDCl 3 ) δ: 178.4, 166.9, 166.7, 145.3, 141.3, 140.7, 139.2, 135.7, 135.0, 134.4, 132.9, 132.6, 132.0, 130.6, 129.8, 129.3, 129.2, 129.1, 129.0, 128.7, 128.5, 128.1, 127.5, 127.2, 127.1, 125.1, 124.5, 123.6, 122.3, 109.6, 52.3, 52.2, 52.1, 43.1, 41.1. HRMS (ESI) m/z calcd for C 38 H 30 + 5 (M+H) + 580.2119, found 580.2122. 2'-methoxy-8'-(4-methoxyphenyl)-1-methyl-10'H-spiro[indoline-3,9'-phenanthre n]-2-one (3ac): white solid, isolated yield 61% (55 mg); mp: 203.8-204.3 o C 26

(uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.81 (d, J = 7.5 Hz, 1H), 7.75 (d, J = 8.5Hz,1H), 7.36-7.33 (m, 2H), 7.22-7.19(m, 1H), 6.99-6.93 (m, 3H), 6.73 (t, J = 7.5 Hz, 1H), 6.65 (d, J=7.5 Hz, 1H), 6.58 (s, 1H), 6.46 (d, J = 7.0 Hz, 1H), 6.30 (dd, J = 8.0 Hz,2.5 Hz, 1H), 5.74 (dd, J = 8.5 Hz, 2.0Hz, 1H), 3.78 (d,j= 2 Hz,6H), 3.61 (d, J=15.0Hz, 1H), 2.65 (s, 3H), 2.47(d, J=14.5 Hz,1H); 13 CMR (125 MHz, CDCl 3 ) δ: 179.0, 159.3, 158.4, 141.9, 141.6, 135.7, 134.5, 133.6, 133.4, 133.3, 131.6, 130.7, 130.1, 128.0, 127.7, 127.6, 125.7, 123.6, 123.1, 122.0, 113.7, 113.3, 113.1, 111.3, 108.1,55.2,52.5, 41.3, 25.9. HRMS (ESI) m/z calcd for C 30 H 26 + 3 (M+H) + 448.1907, found 448.1910. 2'-fluoro-8'-(4-fluorophenyl)-1-methyl-10'H-spiro[indoline-3,9'-phenanthren]-2-o ne (3ae): white solid, isolated yield 55% (47 mg); mp: 183.6-185.1 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 7.86 (d, J = 7.5 Hz, 1H), 7.79 (dd, J=7.5 Hz, 5.5Hz, 1H), 7.39 (t, J = 7.5 Hz, 2H), 7.24-7.21 (m, 1H), 7.13-7.07 (m, 2H), 7.01 (d, J = 7.5Hz, 1H), 6.79-6.74 (m, 2H), 6.67 (d, J = 7.5 Hz, 1H), 6.48-6.42 (m, 2H), 5.79 (t, J = 1.0 Hz, 1H), 3.61 (d, J = 10.0 Hz, 1H), 2.68 (s, 3H), 2.51 (d, J = 15.0 Hz, 1H); 13 CMR (125 MHz, CDCl 3 ) δ: 178.6, 162.4 (d, J = 246.5 Hz), 161.9 (d, J = 244.8 Hz), 141.7, 141.1, 136.5 (d, J = 3.2 Hz), 135.2 (d, J =8.0 Hz), 135.1, 133.8, 132.9, 132.3 (d, J = 7.9 Hz), 131.3, 131.0, 130.7 (d, J = 7.9 Hz), 128.4, 127.9, 126.3 (d, J = 27

8.3 Hz), 123.9, 123.5, 122.2, 115.5 (d, J = 21.6 Hz), 115.0, 114.8 (d, J = 8.7 Hz), 114.6, 112.4 (d, J = 20.9 Hz), 108.4, 52.3, 40.9, 25.9. HRMS (ESI) m/z calcd for C 28 H 20 F 2 + (M+H) + 424.1508, found 424.1509. 1-benzyl-8'-(3,5-dimethylphenyl)-1',3'-dimethyl-10'H-spiro[indoline-3,9'-phenant hren]-2-one (3cj): yellow solid, isolated yield 65% (68 mg); mp: 115.4-116.3 o C (uncorrected); 1 H MR (500 MHz, CDCl 3 ) δ: 8.30 (dd, J = 8.5 Hz, 2.5 Hz, 1H), 7.88 (dd, J = 7.0 Hz, 0.5 Hz, 1H), 7.52 (s, 1H), 7.37 (t, J = 8.0 Hz, 1H), 7.29 (t, J = 7.5 Hz, 2H), 7.24-7.18 (m, 3H), 7.09-7.04 (m, 3H), 6.96 (s, 1H), 6.89 (s, 1H), 6.69 (t, J = 7.5 Hz, 1H), 6.53 (d, J = 7.5 Hz, 1H), 6.46 (d, J = 7.5 Hz, 1H), 5.51 (s, 1H), 4.76 (d, J = 16.0 Hz, 1H), 3.52 (d, J = 15.5 Hz, 1H), 3.39 (d, J = 15.0 Hz, 1H), 2.72 (d, J = 15.0 Hz, 1H), 2.43 (s, 3H), 2.40 (s, 3H), 2.06 (s, 3H), 1.89 (s, 3H); 13 CMR (125 MHz, CDCl 3 ) δ: 179.5, 142.1, 141.1, 140.6, 137.1, 136.5, 136.4, 136.3, 135.6, 135.5, 135.0, 134.0, 133.9, 130.9, 130.4, 128.7, 128.6, 128.2, 128.1, 127.6, 127.5, 127.4, 127.3, 127.2, 124.0, 123.5, 123.2, 122.0, 109.0, 52.4, 43.2, 37.0, 21.4 (double), 21.1, 19.3. HRMS (ESI) m/z calcd for C 38 H 34 + (M+H) + 520.2635, found 520.2639. 28

The mixture of 1,3'-dimethyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-oneand (7) 1-methyl-8'-(p-tolyl)-10'H-spiro[indoline-3,9'-phenanthren]-2-one (7 ): white solid, isolated yield 42% (40 mg); 1 H MR (500 MHz, CDCl 3 ) δ: 7.89 (t, J = 8.0 Hz, 3H), 7.83 (d, J = 8.0 Hz, 2H), 7.73 (d, J =8.0 Hz, 1H), 7.45-7.36 (m, 7H), 7.33 (d, J = 7.5 Hz, 2H),7.24-7.15 (m, 11H), 7.06-7.01 (m, 5H), 6.86 (s, 1H), 6.78-6.70 (m, 4H), 6.64 (t, J = 7.5 Hz, 3H), 6.58 (d, J = 7.5 Hz, 2H), 6.44 (d, J = 7.5 Hz, 1H), 6.39 (d, J = 7.5 Hz, 2H), 5.83 (d, J = 7.0 Hz, 1H), 5.72 (d, J = 7.5 Hz, 2H), 3.65-3.59 (m, 3H), 2.59-2.58 (m, 9H), 2.52 (d, J = 14.5 Hz, 2H), 2.48 (d, J = 15.0 Hz, 1H), 2.32 (s, 3H), 2.30 (s, 6H); 13 CMR (125 MHz, CDCl 3 ) δ: 179.0, 178.9, 142.0, 141.9, 137.9, 136.5, 135.9, 135.8, 135.0, 134.3, 133.4, 133.0, 132.8, 131.5, 131.0, 130.3, 130.2, 129.3, 129.0, 128.9, 128,7, 128.6,128.5, 128.0, 127.9, 127.7,(triple), 127.0, 126.3, 125.8, 124.5, 124.4, 123.9, 123.7, 123.6, 122.0, 108.2, 52.5,(double), 41.1, 41.0, 25.9, 25.8, 21.1, 21.0. 29

(E) Reference [1] (a) Sharma, U. K.; Sharma,.; Kumar,Y.; Singh, B. K.; Van der Eycken, E. V. Chem. Eur. J. 2016, 22, 481; (b) Kong, W.; Wang, Q.; Zhu, J. Angew. Chem. Int. Ed. 2016, 55, 9714; (c) Vachhani, D. D.; Butani, H. H.; Sharma,.; Bhoya, U. C.; Shah, A. K.; Van der Eycken, E. V. Chem. Commun. 2015, 51, 14862. [2] Chavan, S. P.; Pathak, A. B.; Pandey, A.; Kalkote, U. R. Synth. Commun. 2007, 37, 4253. [3] Yoon, H.; Lossouarn, A.; Landau, F; Lautens, M. rg. Lett. 2016, 18, 6324. [4]Wang, H.-L.; Hu, R.-B.; Zhang, H.; Zhou, A.-X.; Shang, D. rg. Lett. 2013, 15, 5203. 30

(F) Spectra 1-methyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3aa) 31

1-ethyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3ba) Et Et 32

1-benzyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3ca) 33

1-(4-fluorobenzyl)-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3da) F F 34

1-(4-methylbenzyl)-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3ea) 35

1-benzyl-5-methyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3fa) 36

1-benzyl-6-methyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3ga) 37

1-benzyl-6-methoxy-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3ha) Me Me 38

1-benzyl-5-chloro-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3ia) Cl Cl 39

1-benzyl-6-chloro-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3ja) Cl Cl 40

1-benzyl-5-fluoro-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3ka) F F 41

1-benzyl-8'-phenyl-5-(trifluoromethyl)-10'H-spiro[indoline-3,9'-phenanthren]-2- one (3la) F 3 C F 3 C 42

1-benzyl-2-oxo-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthrene]-5-carbonitrile( 3ma) C C 43

1-benzyl-6'-fluoro-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3na) F F 44

1-benzyl-6'-methoxy-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3oa) Me Me 45

1-benzyl-8'-fluoro-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3pa) 46

1-benzyl-2'-methyl-8'-(p-tolyl)-10'H-spiro[indoline-3,9'-phenanthren]-2-one (3cb) 47

1-benzyl-2'-methoxy-8'-(4-methoxyphenyl)-10'H-spiro[indoline-3,9'-phenanthren ]-2-one (3cc) Me Me Me Me 48

1-benzyl-2'-(dimethylamino)-8'-(4-(dimethylamino)phenyl)-10'H-spiro[indoline-3,9'-phenanthren]-2-one(3cd) (Me) 2 (Me) 2 (Me) 2 (Me) 2 49

1-benzyl-2'-fluoro-8'-(4-fluorophenyl)-10'H-spiro[indoline-3,9'-phenanthren]-2-o ne (3ce) F F F F 50

1-benzyl-2'-chloro-8'-(4-chlorophenyl)-10'H-spiro[indoline-3,9'-phenanthren]-2- one (3cf) Cl Cl Cl Cl 51

1-benzyl-2'-(trifluoromethyl)-8'-(4-(trifluoromethyl)phenyl)-10'H-spiro[indoline- 3,9'-phenanthren]-2-one(3cg) F 3 C CF 3 F 3 C CF 3 52

8'-([1,1'-biphenyl]-4-yl)-1-benzyl-2'-phenyl-10'H-spiro[indoline-3,9'-phenanthren ]-2-one (3ch) Ph Ph Ph Ph 53

1-benzyl-8'-(4-(methoxycarbonyl)phenyl)-2-oxo-10'H-spiro[indoline-3,9'-phenant hrene]-2'-carboxylate (3ci) MeC CMe MeC CMe 54

2'-methoxy-8'-(4-methoxyphenyl)-1-methyl-10'H-spiro[indoline-3,9'-phenanthre n]-2-one (3ac) Me Me Me Me 55

2'-fluoro-8'-(4-fluorophenyl)-1-methyl-10'H-spiro[indoline-3,9'-phenanthren]-2-o ne (3ae) F F F F 56

1-benzyl-8'-(3,5-dimethylphenyl)-1',3'-dimethyl-10'H-spiro[indoline-3,9'-phenant hren]-2-one (3cj) 57

The mixture of 1,3'-dimethyl-8'-phenyl-10'H-spiro[indoline-3,9'-phenanthren]-2-one (7) and 1-methyl-8'-(p-tolyl)-10'H-spiro[indoline-3,9'-phenanthren]-2-one (7 ) 58

(G) The X-ray Single-Crystal Diffraction Analysis of 3ac (CCDC: 1825599) Me Me Table S2. Crystal data and structure refinement for exp_141. Identification code exp_141 Empirical formula C 30 H 25 3 Formula weight 447.51 Temperature/K 293(2) Crystal system rthorhombic Space group Pbca a/å 16.18095(16) b/å 15.7095(2) c/å 18.00509(19) α/ 90 β/ 90 γ/ 90 Volume/Å 3 4576.81(9) Z 8 ρ calc g/cm 3 1.299 µ/mm -1 0.664 F(000) 1888.0 Crystal size/mm 3 0.3 0.1 0.05 Radiation CuKα (λ = 1.54184) 2Θ range for data collection/ 9.256 to 133.194 Index ranges -19 h 19, -18 k 17, -21 l 21 Reflections collected 62538 Independent reflections 4040 [R int = 0.0794, R sigma = 0.0262] Data/restraints/parameters 4040/0/310 59

Goodness-of-fit on F 2 1.042 Final R indexes [I>=2σ (I)] R 1 = 0.0573, wr 2 = 0.1551 Final R indexes [all data] R 1 = 0.0632, wr 2 = 0.1619 Largest diff. peak/hole / e Å -3 0.21/-0.29 60