Supporting Information

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1 Supporting Information Substrates as Electron Donor Precursors: Synthesis of Naphtho-Fused Oxindoles via Benzannulation of 2-Halobenzaldehydes and Indolin-2-ones Feng-Cheng Jia, Cheng Xu, Zhi-Wen Zhou, Qun Cai, Yan-Dong Wu* and An-Xin Wu* Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, Central China Normal University, Wuhan , P. R. China Table of Contents Pages 1. General S2 2. Starting materials and other preparative substrates......s3 3. Optimization of reaction conditions.s3 4. General procedure for preparation of 3aa-3ah, 3ai-3aq...S3 5. X-ray crystal structures of 3aa, 3bi, 3ci and 3ii......S4-S7 6. Additional control experiments and further discussion of the reaction mechanism.s8-s9 7. Spectral data of substrates 2i-2q and 4,6....S10-S12 8. Spectral data of compounds 3aa-3ah, 3ai-3aq S12-S22 9. Reference....S Appendix: spectral copies of 1 H NMR, and 13 C NMR...S23-S68 -S1-

2 1. General Chemicals and solvents were purchased from commercial suppliers and used without further purification. TLC analysis was performed using pre-coated glass plates. Column chromatography was performed using silica gel ( mesh). IR spectra were recorded on a Perkin-Elmer PE-983 infrared spectrometer as KBr pellets with absorption in cm 1. 1 H NMR spectra were recorded on a Varian Mercury 400 or 600 MHz spectrometer Chemical shifts are reported in ppm, relative to the internal standard of tetramethylsilane (TMS). HRMS were obtained on an Apex-Ultra MS equipped with an electrospray source. Melting points were determined using XT-4 apparatus and not corrected. 2. Starting materials and other preparative substrates 2-bromobenzaldehydes (1a-lj), 2-iodobenzaldehyde (1k) and indolin-2-ones (2a-2h; 2r-2s) were commercially available, N-substituted indolin-2-ones (2i-2q) were prepared according to literature i as an example: A sealed vessel was charged with isatin (735 mg, 5 mmol), MeI (1065 mg, 7.5 mmol), K 2CO 3 (1.38g, 10 mmol) at room temperature, and then solvent DMF (20 ml) was added. The resulting mixture was stirred at 80 C in a sealed vessel under Ar atmosphere, after disappearance of the reactant (monitored by TLC), then added 50 ml water to the mixture, extracted with EtOAc 3 times (3 50 ml). The extract was washed with 30% NaCl solution (V/V), dried over anhydrous Na 2SO 4 and concentrated under reduced pressure. The residue was next dissolved to 30 ml EtOH, hydrazine hydrate (85%, 10 ml) under Ar was added. The mixture was stirred at 90 o C for 24 h. After cooling to room temperature, the solution was concentrated. The residue was diluted with H 2O, and the resulting solution was extracted with EtOAc. The combined organic phases were washed with 30% NaCl solution, dried with Na 2SO 4, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate) to provide 1-methylindolin-2-one 2i as a dark yellow solid. Compounds 4 were prepared according to literature. -S2-

3 To a solution of 2-oxindole (1.33 g, 10 mmol) in methanol was added 2-bromobenzaldehyde (1.85 g, 10 mmol) and catalytic amount of piperidine (85mg, 1mmol). The mixture was heated in 30mL EtOH to reflux for 3 hours and cooled to room temperature, then the solid were filtered and recrystalization from ethanol to afford (E)-3-(2-bromobenzylidene)indolin-2-one (4) as a yellow solid. Compound 6 were prepared according to literature (Cholakova, T.; Vasilev, A.; Ninjo, N.; Dobrev, A. Heterocycl Commun. 2005, 11,181.). 3. Optimization of reaction conditions Table S1: Screening of optimal reaction conditions a entry variation from the standard reaction conditions yield [%] b 1 DMF instead of DMSO 32 2 toluene instead of DMSO trace 3 dioxane instead of DMSO trace o C, 6 h o C a (1.0 equiv) trace 7 2a (1.2 equiv) a (1.4 equiv) a (1.8 equiv) Cs2CO3 (2.5 equiv) Cs2CO3 (3.5 equiv) 83 a Reaction conditions: 1a (0.30 mmol), 2a (0.48 mmol), Cs2CO3 (0.9 mmol) and DMSO (4 ml) under Ar atmosphere at 120 o C for 2 h. b Isolated yield. 4. General procedure for preparation of 3aa-3ah, 3ai-3aq (3aa as an example) General procedure: A sealed tube was charged with 2-bromobenzaldehyde 1a (93 mg, 0.5 mmol), indolin-2-one 2a (106 mg, 0.8 mmol), Cs 2CO 3 (489 mg, 1.5 mmol) at room -S3-

4 temperature, and then dried solvent DMSO (4 ml) was added. The resulting mixture was stirred at 120 C in a sealed vessel under Ar atmosphere, after disappearance of the reactant (monitored by TLC), then added 50mL water to the mixture, extracted with EtOAc 3 times (3 50 ml). The extract was washed with 30% NaCl solution (V/V), dried over anhydrous Na 2SO 4 and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (Petroleum ether / ethyl acetate = 2:1) to yield the desired product 3aa as a yellow solid (85% yield). 5. X-ray crystal structures of 3aa, 3bi, 3ci and 3ii Figure S1 X-ray crystal structure of 3aa. Table S2. Crystal data and structure refinement for compound 3aa (CCDC: ) Empirical formula C 30 H 18 N 2 O 2 Absorption coefficient mm -1 Formula weight F(000) 912 Temperature 296(2) K Crystal size 0.20 x 0.20 x 0.20 mm 3 Wavelength Å Reflections collected Crystal system Orthorhombic Independent reflections 5354 [R(int) = ] Space group Pna2(1) Full-matrix least-squares = Refinement method a = (4) Å on F 2 90 Unit cell b = (15) = dimensions Å 90 Goodness-of-fit on F c = (7) Å = Final R indices [I>2sigma(I)] R1 = , wr2 = Volume (10) Å 3 R indices (all data) R1 = , wr2 = Z 4 Largest diff. peak and hole and e.å -3 Density (calculated) Mg/m 3 -S4-

5 Figure S2 X-ray crystal structure of 3bi. Table S3. Crystal data and structure refinement for compound 3bi (CCDC: ) Empirical formula C 17 H 13 N O Absorption coefficient mm -1 Formula weight F(000) 520 Temperature 296(2) K Crystal size 0.22 x 0.20 x 0.17 mm 3 Wavelength Å Reflections collected Crystal system orthorhombic Independent reflections 4116 [R(int) = ] Space group P2(1)2(1)2(1) Max. and min. transmission and a = (10) Å = 90 Refinement method Full-matrix least-squares on F 2 Unit cell dimensions b = (16) Å = ( 2) Goodness-of-fit on F c = (18) Å = 90 Final R indices [I>2sigma(I)] R1 = , wr2 = Volume (3) Å 3 R indices (all data) R1 = , wr2 = Z 4 Largest diff. peak and hole 0.185and e.å -3 Density (calculated) Mg/m 3 -S5-

6 Figure S3 X-ray crystal structure of 3ci. Table S4. Crystal data and structure refinement for compound 3ci (CCDC: ) Empirical formula C 17 H 13 N O 2 Absorption coefficient mm -1 Formula weight F(000) 276 Temperature 296(2) K Crystal size 0.22 x 0.20 x 0.18 mm 3 Wavelength Å Reflections collected 4188 Crystal system Triclinic Independent reflections 2199 [R(int) = ] Space group P-1 Max. and min. transmission and a = (3) Å = ( 5) Refinement method Full-matrix least-squares on F 2 Unit cell dimensions b = 8.477(3) Å = ) Goodness-of-fit on F c = 9.528(3) Å = (5) Final R indices [I>2sigma(I)] R1 = , wr2 = Volume 635.9(4) Å 3 R indices (all data) R1 = , wr2 = Z 2 Largest diff. peak and hole 0.273and e.å -3 Density (calculated) Mg/m 3 -S6-

7 Figure S4 X-ray crystal structure of 3ii. Table S5. Crystal data and structure refinement for compound 3ii (CCDC: ) Empirical formula C 18 H 15 N O 3 Absorption coefficient mm -1 Formula weight F(000) 616 Temperature 296(2) K Crystal size 0.22 x 0.20 x 0.18 mm 3 Wavelength Å Reflections collected Crystal system Monoclinic Independent reflections 2400 [R(int) = ] Space group P2(1)/n Max. and min. transmission and a = (12) Å = 90 Refinement method Full-matrix least-squares on F 2 Unit cell dimensions b = (12) Å = ( 2) Goodness-of-fit on F c = (4) Å = Final R indices [I>2sigma(I)] R1 = , wr2 = Volume (4) Å 3 R indices (all data) R1 = , wr2 = Z 4 Largest diff. peak and hole and e.å -3 Density (calculated) Mg/m 3 -S7-

8 6. Additional control experiments and further discussion of the reaction mechanism (1) Other organic additives with methylene were tested under the standard conditions, and all cases were shown in the table below. (2) Mixtures of products were formed when different N-substituted indolin-2-ones (2i or 2c) were used as additives. A possible dynamic equilibrium between 4, 5, 5, and 4 was proposed to explain these results from the control experiments in Scheme 4 (4 + 2i as example), and additional control experiment suggest that 5, 5 was also possible cyclization precursor. (3) A phenyl radical-induced aromatic 1,6-hydrogen transfer might invloved in the mechanism (R = H; 3 = 3 ). Two regioisomers would be obtained when 5-substituted 2-bromoaldehyde were used as substrates (R H; 3 3 ). -S8-

9 (4) The mechanism involving Michael addition of enolates A to 4 followed by intermolecular electron transfer is also possible, in other words, 6 was also possible cyclization precursor. Initially, deprotonation of the CH 2 protons within indolin-2-one (2a) generates the eletron-rich enolate anion (A) in the presence of Cs 2CO 3. Most of enolate anion (A) condenses with 2-bromobenzaldehyde, leading to the formation of 4, followed by Michael addition of enolates A to 4. The resulting intermediate 6 would undergo base-promoted homolytic aromatic substitution with the assistance of electrons released from the rest of enolates. -S9-

10 7. Spectral data of substrates 2i-2q; 4. 1-methylindolin-2-one (2i) 1 H NMR (600 MHz, CDCl3): δ = 7.28 (t, J = 7.8 Hz, 1H), 7.23 (d, J = 7.2 Hz, 1H), 7.04 (t, J = 7.8 Hz, 1H), 6.82 (d, J = 7.8 Hz, 1H), 3.51 (s, 2H), 3.20 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 174.7, 144.9, 127.6, 124.2, 124.0, 122.1, 107.9, 35.7, HRMS (ESI): m/z [M + Na] + calcd for C9H9NONa: ; found: ,5-dimethylindolin-2-one (2j) 1 H NMR (600 MHz, CDCl3): δ = 6.87 (s, 1H), 6.80 (d, J = 8.4 Hz, 1H), 6.71 (d, J = 8.4 Hz, 1H), 3.79 (s, 3H), 3.49 (s, 2H), 3.18 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 174.3, 155.5, 138.5, 125.5, 111.8, 111.7, 108.1, 55.7, 36.1, HRMS (ESI): m/z [M + Na] + calcd for C10H11NONa: ; found: methoxy-1-methylindolin-2-one (2k) 1 H NMR (600 MHz, CDCl3): δ = (m, 2H), 6.70 (d, J = 7.8 Hz, 1H), 3.47 (s, 2H), 3.18 (s, 3H), 2.33 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 174.7, 142.5, 131.6, 127.8, 125.0, 124.3, 107.6, 35.8, 26.2, HRMS (ESI): m/z [M + Na] + calcd for C10H11NO2Na: ; found: chloro-1-methylindolin-2-one (2l) 1 H NMR (600 MHz, CDCl3): δ = 7.25 (d, J = 8.4 Hz, 1H), 7.21 (s, 1H), 6.73 (d, J = 7.8 Hz, 1H), 3.50 (s, 2H), 3.19 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 174.0, 143.4, 127.5, 127.3, 125.8, 124.5, 108.7, 35.6, HRMS (ESI): m/z [M + Na] + calcd for C9H8ClNONa: ; found: chloro-1-methylindolin-2-one (2m) 1 H NMR (600 MHz, CDCl3): δ = 7.14 (d, J = 7.2 Hz, 1H), 7.01 (d, J = 7.8 Hz, 1H), 6.81 (s, 1H), 3.48 (s, 2H), 3.19 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 174.6, 146.0, -S10-

11 133.4, 124.9, 122.5, 121.9, 108.6, 35.3, HRMS (ESI): m/z [M + Na] + calcd for C9H8ClNONa: ; found: bromo-1-methylindolin-2-one (2n) 1 H NMR (600 MHz, CDCl3): δ = 7.16 (d, J = 7.2 Hz, 1H), 7.09 (d, J = 7.2 Hz, 1H), 6.96 (s, 1H), 3.46 (s, 2H), 3.18 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 174.4, 146.2, 125.3, 124.8, 123.0, 121.2, 111.4, 35.4, HRMS (ESI): m/z [M + Na] + calcd for C9H8BrNONa: ; found: chloro-1-methylindolin-2-one (2o) 1 H NMR (600 MHz, CDCl3): δ = 7.20 (d, J = 7.8 Hz, 1H), 7.12 (d, J = 7.2 Hz, 1H), 6.94 (t, J = 7.8 Hz, 1H), 3.58 (s, 3H), 3.53 (s, 2H). 13 C NMR (100 MHz, CDCl3): δ = 174.7, 140.7, 130.0, 126.8, 122.9, 122.6, 115.2, 35.8, HRMS (ESI): m/z [M + Na] + calcd for C9H8ClNONa: ; found: propylindolin-2-one (2p) 1 1 H NMR (600 MHz, CDCl3): δ = (m, 2H), 7.02 (t, J = 7.8 Hz, 1H), 6.83 (d, J = 7.2 Hz, 1H), 3.67 (t, J = 7.8 Hz, 2H), 3.52 (s, 2H), (m, 2H), 0.97 (t, J = 7.8 Hz, 3H), 13 C NMR (100 MHz, CDCl3): δ = 174.6, 144.3, 127.5, 124.4, 124.1, 121.8, 108.1, 41.5, 35.8, 20.8, HRMS (ESI): m/z [M +Na] + calcd for C11H13NONa: ; found: (3-phenylpropyl)indolin-2-one (2q) 1 1 H NMR (600 MHz, CDCl3): δ = 7.27 (t, J = 7.8 Hz, 2H), 7.23 (t, J = 8.4 Hz, 2H), 7.19 (d, J = 7.8 Hz, 3H), 7.01 (t, J = 7.8 Hz, 1H), 6.72 (d, J = 7.8 Hz, 1H), 3.74 (t, J = 7.8 Hz, 2H), 3.49 (s, 2H), 2.70 (t, J = 7.8 Hz, 2H), (m, 2H). 13 C NMR (100 MHz, CDCl3): δ = 174.7, 144.2, 140.8, 128.2, 128.1, 127.6, 125.8, 124.4, 124.2, 122.0, 108.1, 39.6, 35.8, 33.2, HRMS (ESI): m/z [M + H] + calcd for C17H18NO: ; found: S11-

12 (E)-3-(2-bromobenzylidene)indolin-2-one (4) 1 H NMR (600 MHz, CDCl3): δ = 9.50 (s, 1H), 7.82 (s, 1H), 7.71 (t, J = 6.0 Hz, 2H), 7.40 (t, J = 7.2 Hz, 1H), (m, 2H), 7.22 (t, J =7.8 Hz, 1H), 6.97 (d, J = 7.8 Hz, 1H), 6.82 (t, J = 7.8 Hz, 1H), 13 C NMR (150 MHz, CDCl3): 170.1, 142.0, 135.7, 135.3, 133.1, 130.8, 130.2, 129.0, 127.2, 124.2, 123.1, 121.8, 121.2, HRMS (ESI): m/z [M + Na] + calcd for C15H10BrNONa: ; found: ,3'-((2-bromophenyl)methylene)bis(indolin-2-one) (6) dr = 10:1.7; 1 H NMR (600 MHz, DMSO-d6): δ = (s, 2H), 7.51 (d, J = 7.8 Hz, 1H), 7.18 (t, J = 7.8 Hz, 2H), 7.13 (t, J = 7.8 Hz, 1H), 7.06 (t, J = 7.8 Hz, 1H), (m, 5H), (m, 2H), 4.41 (d, J = 8.4 Hz, 2H), 4.15 (t, J = 9.0 Hz, 1H); δ = (s, 2H), 7.41 (d, J = 7.2 Hz, 2H), 7.33 (d, J = 7.8 Hz, 2H), 7.23 (t, J = 7.8 Hz, 2H), 6.98 (t, J = 7.2 Hz, 2H), 6.86 (t, J = 7.8 Hz, 2H), 6.74 (d, J = 7.8 Hz, 2H), 4.27 (d, J = 8.4 Hz, 2H), (m, 1H); 13 C NMR (150 MHz, DMSO-d6): 177.2, 177.0, 142.9, 142.6, 138.6, 138.1, 132.7, 132.6, 129.2, 129.1, 128.7, 128.5, 128.1, 128.0, 127.5, 127.1, 126.8, 126.2, 125.1, 125.0, 121.2, 120.9, 109.5, 109.2, 46.8, 46.5, 45.1, HRMS (ESI): m/z [M + Na] + calcd for C23H17BrN2O2Na: ; found: Spectral data of compound 3aa-3ah, 3ai-3aq naphtho[3,2,1-cd]indol-5(4h)-one (3aa) 4 Yield 85% (93.2 mg); yellow solid; mp ; IR (KBr): 3211, 1709, 1662, 1629, 1608, 1525, 1466, 1219, 1134 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = (s, 1H), 8.82 (d, J = 7.8 Hz, 1H), 8.56 (s, 1H), 8.37 (d, J = 7.8 Hz, 1H), 8.27 (d, J = 8.4 Hz, 1H), 7.90 (t, J = 7.8 Hz, 1H), 7.79 (t, J = 7.2 Hz, 1H), 7.66 (t, J = 7.8 Hz, 1H), 7.13 (d, J = 7.2 Hz, 1H); 13 C NMR (150 MHz, DMSO-d6): δ = 168.5, 138.6, 133.1, 131.9, 131.5, 129.4, 129.3, 127.3, 126.5, 125.5, 123.8, 123.7, 122.1, 115.5, HRMS (ESI): m/z [M + Na] + calcd for C15H9NONa: ; found: S12-

13 9-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3ba) 4 Yield 82% (95.6 mg); yellow solid; mp ; IR (KBr): 3184, 1693, 1626, 1605, 1466, 1221, 1191, 1160 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = (s, 1H), 8.51 (s, 1H), 8.46 (s, 1H), 8.17 (t, J = 9.6 Hz, 2H), 7.63 (t, J = 7.8 Hz, 1H), 7.55 (d, J = 7.8 Hz, 1H), 7.14 (d, J = 7.2 Hz, 1H), 2.63 (s, 3H); 13 C NMR (150 MHz, DMSO-d6): δ = 168.6, 139.3, 138.5, 131.5, 131.0, 129.0, 128.8, 126.3, 126.2, 126.1, 124.5, 123.1, 122.2, 115.3, 106.5, HRMS (ESI): m/z [M + Na] + calcd for C16H11NONa: ; found: methoxynaphtho[3,2,1-cd]indol-5(4H)-one (3ca) Yield 74% (92.2 mg); yellow solid; mp ; IR (KBr): 3185, 1690, 1604, 1518, 1464, 1419, 1354, 1244, 1214, 1158, 1132, 1061,1027 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = (s, 1H), 8.46 (s, 1H), 8.29 (d, J = 8.4 Hz, 1H), 8.25 (d, J = 8.4 Hz, 1H), 8.20 (s, 1H), 7.62 (t, J = 7.8 Hz, 1H), (m, 1H), 7.11 (d, J= 7.2 Hz, 1H), 4.07 (s, 3H). 13 C NMR (100 MHz, DMSO-d6): δ = 168.3, 159.9, , 133.0, 128.4, 127.4, 126.2, 125.7, 122.7, 122.4, 117.4, 115.6, 106.4, 104.5, HRMS (ESI): m/z [M + Na] + calcd for C16H11NO2Na: ; found: fluoronaphtho[3,2,1-cd]indol-5(4H)-one (3da) Yield 72% (85.4 mg); yellow solid; mp >300 ; IR (KBr): 3178, 1718, 1614, 1535, 1467, 1443, 1230, 1208, 1177, 1061 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = (s, 1H), 8.60 (d, J = 10.2 Hz, 1H), 8.53 (s, 1H), 8.40 (t, J = 7.2 Hz, 1H), 8.23 (d, J = 8.4 Hz, 1H), 7.65 (t, J = 9.0 Hz, 1H), 7.61 (t, J = 7.8 Hz, 1H), 7.09 (d, J = 6.6 Hz, 1H). 13 C NMR (100 MHz, DMSO-d6): δ = 168.0, 163.3, 160.8, 138.2, 134.3, , , 133.1, 129.8, 129.1, 125.9, , , 122.1, 116.3, 116.0, 115.7, 108.9, 108.7, HRMS (ESI): m/z [M + Na] + calcd for C15H8FNONa: ; found: chloronaphtho[3,2,1-cd]indol-5(4H)-one (3ea) 4 Yield 68% (86.3 mg); yellow solid; mp >300 ; IR (KBr): 3181, 1725, 1631, 1600, 1512, 1466, 1432, 1218, 1158, 1099,1062 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = (s, 1H), 8.80 (s, 1H), 8.47 (s, 1H), 8.30 (d, J = 9.0 Hz, 1H), 8.22 (d, J = 8.4 Hz, -S13-

14 1H), 7.74 (d, J = 7.8 Hz, 1H), 7.60 (d, J = 7.2 Hz, 1H), 7.08 (d, J = 6.6 Hz, 1H). 13 C NMR (100 MHz, DMSO-d6): δ = 167.9, 138.3, 134.1, 133.4, 132.3, 131.4, 129.4, 127.3, 125.6, 125.4, 123.0, 122.1, 115.6, HRMS (ESI): m/z [M + Na] + calcd for C15H8ClNONa: ; found: thieno[3',2':4,5]benzo[1,2,3-cd]indol-5(4h)-one(3fa) Yield 86% (96.9 mg); yellow solid; mp ; IR (KBr): 3177, 1707, 1635, 1585, 1494, 1465, 1327, 1308, 1252, 1178 cm -1 ; 1 H NMR (400 MHz, DMSO-d6): δ = (s, 1H), 8.63 (s, 1H), (m, 2H), 7.97 (d, J = 8.0 Hz, 1H), 7.55 (t, J = 8.0 Hz, 1H), 7.00 (d, J = 7.2 Hz, 1H), 13 C NMR (100 MHz, DMSO-d6): δ = 168.1, 139.3, 138.3, 138.0, 132.2, 128.9, 124.5, 123.3, 122.4, 122.2, 119.9, 116.0, HRMS (ESI): m/z [M + Na] + calcd for C13H7NOSNa: ; found: methylnaphtho[3,2,1-cd]indol-5(4H)-one (3ab) Yield 82% (95.6 mg); yellow solid, mp ; IR (KBr): 3169, 1687, 1629, 1603, 1529, 1486, 1467, 1448, 1260, 1228, 1204, 1146 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = 9.65 (s, 1H), 7.55 (d, J = 8.4 Hz, 1H), 7.22 (s, 1H), 7.08 (d, J = 7.8 Hz, 1H), 6.60 (t, J = 7.8 Hz, 1H), 6.51 (t, J = 7.8 Hz, 1H), 6.11 (d, J = 7.2 Hz, 1H), 5.77 (d, J = 7.2 Hz, 1H), 1.67 (s, 3H). 13 C NMR (150 MHz, DMSO-d6): δ = 168.3, 136.9, 133.8, 132.7, 132.2, 131.7, 128.7, 127.7, 126.6, 126.4, 126.2, 125.8, 125.5, 122.7, 106.6, HRMS (ESI): m/z [M + Na] + calcd for C16H11NONa: ; found: methoxynaphtho[3,2,1-cd]indol-5(4H)-one (3ac) Yield 77% (95.9 mg); brown solid, mp ; IR (KBr): 3164, 1700, 1636, 1474, 1428, 1261, 1227, 1144, 1057 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = 9.60 (s, 1H), 8.18 (d, J = 8.4 Hz, 1H), 7.36 (s, 1H), 7.15 (d, J = 7.8 Hz, 1H), 6.67 (t, J = 7.8 Hz, 1H), 6.55 (t, J = 7.2 Hz, 1H), 5.92 (d, J = 7.8 Hz, 1H), 5.85 (d, J = 7.8 Hz, 1H), 2.89 (s, 3H). 13 C NMR (150 MHz, DMSO-d6): δ = 168.4, 153.2, 133.2, 131.8, 131.5, 131.3, 129.2, 127.7, 127.3, 126.5, 125.8, 123.3, 117.1, 109.0, 107.1, HRMS (ESI): m/z [M + Na] + calcd for C16H11NO2Na: ; found: fluoronaphtho[3,2,1-cd]indol-5(4H)-one (3ad) -S14-

15 Yield 74% (87.8 mg); yellow solid, mp ; IR (KBr): 3186, 1700, 1637, 1608, 1471, 1438, 1317, 1222, 1201, 1135, 1040 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = (s, 1H), 8.83 (d, J = 7.8 Hz, 1H), 8.59 (s, 1H), 8.40 (d, J = 7.8 Hz, 1H), 7.93 (t, J = 7.8 Hz, 1H), 7.83 (t, J = 7.2 Hz, 1H), (m, 1H), 7.04 (d, J = 6.0 Hz, 1H); 13 C NMR (150 MHz, DMSO-d6): δ = 168.3, 155.9, 154.3, 134.6, 133.2, 132.0, 129.8, 128.9, 127.6, 127.4, 126.6, 126.5, 125.3, 123.0, 115.4, 115.3, 114.4, 114.3, HRMS (ESI): m/z [M + Na] + calcd for C15H8FNONa: ; found: chloronaphtho[3,2,1-cd]indol-5(4H)-one (3ae) Yield 72% (91.3 mg); yellow solid, mp >300 ; IR (KBr): 3175, 1714, 1627, 1532, 1484, 1449, 1426, 1219, 1017 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = (s, 1H), 9.54 (d, J = 8.4 Hz, 1H), 8.47 (s, 1H), 8.28 (d, J = 7.8 Hz, 1H), 7.83 (t, J = 7.8 Hz, 1H), 7.74 (t, J = 7.2 Hz, 1H), 7.57 (d, J = 7.8 Hz, 1H), 6.98 (d, J = 7.8 Hz, 1H). 13 C NMR (150 MHz, DMSO-d6): δ = 167.8, 137.9, 133.9, 132.4, 131.6, 130.6, 129.4, 128.2, 127.5, 125.6, 125.3, 123.6, 122.7, 122.1, HRMS (ESI): m/z [M + Na] + calcd for C15H8ClNONa: ; found: nitronaphtho[3,2,1-cd]indol-5(4H)-one (3af) Yield 54% (71.3 mg); yellow solid, mp >300 ; IR (KBr): 3164, 1703, 1627, 1604, 1515, 1485, 1356, 1320, 1224, 1197 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = (s, 1H), 7.39 (s, 1H), 7.15 (d, J = 7.2 Hz, 1H), 6.86 (d, J = 7.8 Hz, 2H), 6.61 (t, J = 7.8 Hz, 2H), 5.89 (d, J = 7.8 Hz, 1H). 13 C NMR (150 MHz, DMSO-d6): δ = 168.1, 142.3, 141.3, 134.2, 132.7, 129.9, 129.2, 128.3, 127.5, 127.3, 125.0, 124.2, 122.6, 117.4, HRMS (ESI): m/z [M + Na] + calcd for C15H8N2O3Na: ; found: chloronaphtho[3,2,1-cd]indol-5(4H)-one (3ag) Yield 70% (88.8 mg); yellow solid, mp >300 ; IR (KBr): 3179, 1712, 1630, 1610, 1526, 1489, 1452, 1215, 1172, 1067 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = 11.0 (s, 1H), 8.75 (d, J = 7.8 Hz, 1H), 8.49 (s, 1H), 8.31 (d, J = 8.4 Hz, 1H), 8.27 (s, 1H), 7.87 (t, J = 7.8 Hz, 1H), 7.78 (t, J = 7.8 Hz, 1H), 7.03 (s, 1H). 13 C NMR (150 MHz, DMSO-d6): δ = 168.3, 139.9, 134.0, 133.4, 131.9, 130.6, 129.5, 127.7, 126.9, 124.7, 124.0, 120.7, 114.9, HRMS (ESI): m/z [M + Na] + calcd for C15H8ClNONa: ; found: S15-

16 2-bromonaphtho[3,2,1-cd]indol-5(4H)-one (3ah) Yield 56% (83.5 mg); yellow solid, mp >300 ; IR (KBr): 3177, 1710, 1623, 1525, 1487, 1451, 1219, 1172, 1142, 1086 cm -1 ; 1 H NMR (600 MHz, DMSO-d6): δ = (s, 1H), 8.74 (d, J = 7.8 Hz, 1H), 8.48 (s, 1H), 8.41 (s, 1H), 8.28 (d, J = 7.2 Hz, 1H), 7.83 (t, J = 7.2 Hz, 1H), 7.74 (t, J = 7.2 Hz, 1H), 7.12 (s, 1H). 13 C NMR (100 MHz, DMSO-d6): δ = 167.9, 139.7, 133.2, 131.7, 130.3, 129.4, 127.6, 127.2, 126.8, 124.6, 123.9, 122.3, 120.8, 117.8, HRMS (ESI): m/z [M + Na] + calcd for C15H8BrNONa: ; found: methylnaphtho[3,2,1-cd]indol-5(4H)-one (3ai) 2 Yield 74% (86.3 mg); yellow solid, mp ; IR (KBr): 1694, 1618, 1526, 1493, 1466, 1443, 1379, 1315, 1285, 1256, 1213 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.42 (d, J = 7.8 Hz, 1H), 8.17 (s, 1H), 7.96 (d, J = 7.8 Hz, 1H), 7.88 (d, J = 8.4 Hz, 1H), 7.69 (t, J = 7.8 Hz, 1H), 7.58 (t, J = 7.8 Hz, 1H), 7.45 (t, J = 7.8 Hz, 1H), 6.79 (d, J = 7.2 Hz, 1H), 3.34 (s, 3H), 13 C NMR (100 MHz, CDCl3): δ = 167.5, 139.8, 133.0, 131.6, 131.5, 128.7, 128.4, 126.7, 126.6, 126.1, 124.6, 123.2, 121.1, 115.7, 104.7, HRMS (ESI): m/z [M + Na] + calcd for C16H11NONa: ; found: Yield 73% (90.3 mg); 4,9-dimethylnaphtho[3,2,1-cd]indol-5(4H)-one (3bi) 2 yellow solid, mp ; IR (KBr): 1695, 1615, 1492, 1463, 1383, 1315, 1282, 1257, 1211, 1177, 1062 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.19 (s, 1H), 8.16 (s, 1H), 7.88 (d, J = 7.8 Hz, 1H), 7.85 (d, J = 7.8 Hz, 1H), 7.46 (t, J = 7.8 Hz, 1H), 7.39 (d, J = 8.4 Hz, 1H), 6.81 (d, J = 7.2 Hz, 1H), 3.36 (s, 3H), 2.57 (s, 3H). 13 C NMR (150 MHz, CDCl3): δ = 167.7, 139.9, 139.2, 131.8, 131.3, 131.0, 128.6, 128.2, 126.6, 125.9, 123.8, 123.0, 121.4, 115.7, 104.7, 26.2, HRMS (ESI): m/z [M + Na] + calcd for C17H13NONa: ; found: S16-

17 9-methoxy-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3ci) 2 Yield 67% (88.2 mg); yellow solid, mp ; IR (KBr): 1693, 1616, 1523, 1496, 1465, 1430, 1302, 1244, 1201, 1151, 1064, 1039 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.04 (s, 1H), (m, 2H), 7.65 (s, 1H), 7.41 (t, J = 7.8 Hz, 1H), (m, 1H), 6.79 (d, J = 7.2 Hz, 1H), 3.96 (s, 3H), 3.35 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 167.4, 159.8, 139.6, 133.3, 132.7, 127.6, 127.4, 126.3, 125.3, 122.1, 121.5, 117.0, 115.5, 104.7, 103.8, 55.4, HRMS (ESI): m/z [M + H] + calcd for C17H14NO2: ; found: fluoro-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3di) 2 Yield 68% (85.4 mg); yellow solid, mp ; IR (KBr): 1691, 1617, 1533, 1467, 1447, 1320, 1287, 1256, 1221, 1184, 1065, 1036 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.30 (s, 1H), (m, 1H), (m, 1H), 7.92 (d, J = 8.4 Hz, 1H), 7.58 (t, J = 7.8 Hz, 1H), (m, 1H), 6.98 (d, J = 7.2 Hz, 1H), 3.45 (s, 3H); 13 C NMR (150 MHz, CDCl3): δ = 167.6, 163.6, 162.0, 140.3, , , , , , 126.4, , , 124.5, 121.8, 116.4, 116.2, 115.9, 108.7, 108.6, 105.5, HRMS (ESI): m/z [M + Na] + calcd for C16H10FNONa: ; found: chloro-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3ei) Yield 64% (85.7 mg); yellow solid, mp ; IR (KBr): 1696, 1619, 1595, 1508, 1464, 1434, 1385, 1317, 1289, 1252, 1209, 1063, 1034 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.33 (s, 1H), 8.15 (s, 1H), 7.91 (d, J = 9.0 Hz, 1H), 7.83 (d, J = 8.4 Hz, 1H), (m, 2H), 6.92 (d, J = 7.2 Hz, 1H), 3.42 (s, 3H), 13 C NMR (150 MHz, CDCl3): δ = 167.3, 140.1, 135.1, 132.8, 132.6, 131.4, 128.9, 127.5, 126.0, 125.4, 125.1, 123.0, 121.6, 115.7, 105.5, HRMS (ESI): m/z [M + Na] + calcd for C16H10ClNONa: ; found: S17-

18 4-methylthieno[3',2':4,5]benzo[1,2,3-cd]indol-5(4H)-one (3fi) Yield 77% (92.2 mg); yellow solid, mp ; IR (KBr): 1684, 1627, 1498, 1463, 1345, 1296, 1270, 1228, 1207, 1093, 1057 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.40 (s, 1H), 7.93 (d, J = 5.4 Hz, 1H), 7.83 (d, J = 5.4 Hz, 1H), 7.78 (d, J = 8.4 Hz, 1H), 7.52 (t, J = 7.8 Hz, 1H), 6.89 (d, J = 7.2 Hz, 1H), 3.44 (s, 3H), 13 C NMR (150 MHz, CDCl3): δ = 167.8, 140.1, 139.8, 138.6, 130.6, 128.6, 124.7, 123.3, 122.0, 121.9, 120.0, 116.7, 104.2, HRMS (ESI): m/z [M + Na] + calcd for C14H9NOSNa: ; found: methylindolo[3,4-gh]isoquinolin-5(4H)-one (3gi) Yield 75% (87.8 mg); yellow solid, mp ; IR (KBr): 1694, 1619, 1493, 1441, 1277, 1251, 1147, 1072 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 9.90 (s, 1H), 8.79 (d, J = 4.8 Hz, 1H), 8.22 (s, 1H), 8.09 (d, J = 8.4 Hz, 1H), 7.89 (d, J = 5.4 Hz, 1H), 7.65 (t, J = 7.8 Hz, 1H), 6.99 (d, J = 7.2 Hz, 1H), 3.44 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 166.6, 147.3, 145.3, 140.3, 136.9, 130.1, 128.9, 125.5, 125.4, 124.3, 123.7, 121.5, 115.4, 105.8, HRMS (ESI): m/z [M + H] + calcd for C15H11N2O: ; found: methoxy-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3hi) 2 Yield 29% (38.2 mg); yellow solid, mp ; IR (KBr): 1710, 1620, 1531, 1493, 1460, 1435, 1321, 1259, 1237, 1166, 1123, 1020 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.36 (d, J = 9.0 Hz, 1H), 8.15 (s, 1H), 7.88 (d, J = 8.4 Hz, 1H), 7.50 (t, J = 7.8 Hz, 1H), (m, 2H), 6.83 (d, J = 7.2 Hz, 1H), 3.95 (s, 3H), 3.40 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 167.5, 158.0, 139.9, 134.6, 128.5, 126.2, 126.1, 125.9, 125.2, 124.5, 120.3, 119.5, 115.4, 111.1, 104.0, 55.4, HRMS (ESI): m/z [M + Na] + calcd for C17H13NO2Na: ; found: methoxy-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3hi ) Yield 37% (48.7 mg); yellow solid, mp ; IR (KBr): 1699, 1603, 1493, 1457, 1323, 1287, 1257, 1090, 1032 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.75 (d, J = 8.4 Hz, 1H), 8.31 (s, 1H), 7.67 (d, J = 7.8 Hz, 1H), (m, 2H), 7.20 (d, J = 7.8 Hz, 1H), 6.92 (d, J = 7.2 Hz, 1H), 4.12 (s, 3H), 3.43 (s, 3H). 13 C NMR (150 MHz, CDCl3): δ = 167.5, 159.0, 139.6, 135.4, 128.3, 127.1, 127.0, 126.1, 125.6, 124.3, 122.4, -S18-

19 122.3, 121.5, 109.8, 104.8, 55.5, HRMS (ESI): m/z [M + H] + calcd for C17H14NO2: ; found: ,9-dimethoxy-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3ii) Yield 35% (51.3 mg); yellow solid, mp ; IR (KBr): 1692, 1618, 1523, 1482, 1442, 1365, 1322, 1256, 1211, 1156, 1044 cm -1 ; 1 H NMR (400 MHz, CDCl3): δ = 8.09 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.69 (s, 1H), 7.48 (t, J = 7.6 Hz, 1H), 7.24 (s, 1H), 6.84 (d, J = 6.8 Hz, 1H), 4.09 (s, 3H), 4.03 (s, 3H), 3.41 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 167.7, 150.9, 149.0, 140.0, 128.1, 127.9, 127.1, 125.5, 125.4, 122.9, 120.8, 115.3, 110.4, 104.0, 103.0, 56.02, 55.98, HRMS (ESI): m/z [M + Na] + calcd for C18H15NO3Na: ; found: ,10-dimethoxy-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one(3ii ) Yield 25% (36.7 mg); yellow solid, mp ; IR (KBr): 1692, 1617, 1593, 1528, 1459, 1421, 1381, 1277, 1185, 1148, 1122, 1066, 1026 cm -1 ; 1 H NMR (400 MHz, CDCl3): δ = 8.74 (d, J = 8.8 Hz, 1H), 8.32 (s, 1H), 7.87 (d, J = 8.8 Hz, 1H), 7.57 (t, J = 8.0 Hz, 1H), 7.37 (d, J = 8.4 Hz, 1H), 7.00 (d, J = 6.8 Hz, 1H), 4,06 (s, 3H), 4.04 (s, 3H), 3.46 (s, 3H), 13 C NMR (100 MHz, CDCl3): δ = 167.4, 153.1, 146.9, 139.7, 129.0, 128.6, 128.3, 127.5, 126.7, 125.4, 123.4, 122.0, 121.3, 113.0, 105.3, 60.0, 56.4, HRMS (ESI): m/z [M + Na] + calcd for C18H15NO3Na: ; found: chloro-5-methyldibenzo[cd,f]indol-4(5H)-one (3ji) Yield 30% (40.2 mg); yellow solid, mp ; IR (KBr): 1703, 1622, 1514, 1489, 1467, 1442, 1318, 1285, 1255, 1089, 1070, 1033 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.49 (d, J = 8.4 Hz, 1H), 8.24 (s, 1H), 8.04 (s, 1H), 8.01 (d, J = 8.4 Hz, 1H), (m, 1H), 7.62 (t, J = 7.8 Hz, 1H), 6.98 (d, J = 7.2 Hz, 1H), 3.46 (s, 3H). 13 C NMR (150 MHz, CDCl3): δ = 167.4, 140.4, 134.3, 132.9, 130.5, 130.2, 129.4, 129.3, , , 125.7, 124.9, 121.5, 115.9, 105.3, HRMS (ESI): m/z [M + H] + calcd for C16H11ClNO: ; found: S19-

20 10-chloro-5-methyldibenzo[cd,f]indol-4(5H)-one (3ji ) Yield 42% (56.2 mg); yellow solid, mp ; IR (KBr): 1700, 1620, 1590, 1438, 1380, 1308, 1279, 1130, 1031 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 9.21 (d, J = 8.4 Hz, 1H), 8.36 (s, 1H), 8.05 (d, J = 7.8 Hz, 1H), 7.84 (d, J = 7.2 Hz, 1H), 7.62 (t, J = 7.8 Hz, 1H), 7.57 (t, J = 7.8 Hz, 1H), 7.05 (d, J = 7.8 Hz, 1H), 3.47 (s, 3H). 13 C NMR (150 MHz, CDCl3): δ = 166.8, 139.8, 135.9, 132.8, 132.3, 131.5, 128.8, 128.2, 127.2, 126.6, 126.0, 125.7, 122.0, 121.0, 105.6, HRMS (ESI): m/z [M + H] + calcd for C16H11ClNO: ; found: ,4-dimethylnaphtho[3,2,1-cd]indol-5(4H)-one (3aj) 2 Yield 74% (91.5 mg); yellow solid, mp ; IR (KBr): 1688, 1619, 1530, 1491, 1450, 1379, 1312, 1254, 1113, 1019 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.61 (d, J = 8.4 Hz, 1H), 8.08 (s, 1H), 7.93 (d, J = 7.2 Hz, 1H), 7.65 (t, J = 7.2 Hz, 1H), 7.56 (t, J = 7.2 Hz, 1H), 7.15 (d, J = 7.2 Hz, 1H), 6.65 (d, J = 7.2 Hz, 1H), 3.30 (s, 3H), 2.80 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 167.0, 138.0, 133.7, 133.0, 131.9, 130.8, 128.9, 128.3, 126.9, 126.4, 125.8, 125.3, 124.9, 121.7, 104.7, 26.1, HRMS (ESI): m/z [M + Na] + calcd for C17H13NONa: ; found: methoxy-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3ak) Yield 65% (85.6 mg); yellow solid, mp ; IR (KBr): 1686, 1623, 1476, 1430, 1318, 1260, 1230, 1059, 1035 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 9.25 (d, J = 8.4 Hz, 1H), 8.25 (s,1h), 7.99 (d, J = 8.4 Hz, 1H), 7.70 (t, J = 7.8 Hz, 1H), 7.59 (t, J = 7.8 Hz, 1H), 6.71 (d, J = 7.8 Hz, 1H), 6.62 (d, J = 7.8 Hz, 1H), 3.97 (s, 3H), 3.32 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 167.1, 154.0, 133.1, 132.8, 131.6, 131.2, 128.8, 128.0, 127.5, 126.1, 124.8, 122.3, 117.2, 107.4, 105.0, 55.7, HRMS (ESI): m/z [M + Na] + calcd for C17H13NO2Na: ; found: S20-

21 1-chloro-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3al) Yield 70% (93.7 mg); yellow solid, mp ; IR (KBr): 1702, 1612, 1530, 1491, 1451, 1427, 1375, 1312, 1252, 1100, 1079 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 9.57 (d, J = 8.4 Hz, 1H), 8.17 (s,1h), 7.99 (d, J = 7.8 Hz, 1H), 7.74 (t, J = 7.8 Hz, 1H), 7.66 (t, J = 7.2 Hz, 1H), 7.42 (d, J = 7.2 Hz, 1H), 6.71 (d, J = 7.8 Hz, 1H), 3.33 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 166.5, 138.6, 133.6, 131.8, 131.2, 130.7, 128.9, 128.3, 127.1, 126.2, 124.3, 124.0, 122.9, 122.5, 105.4, HRMS (ESI): m/z [M + Na] + calcd for C16H10ClNONa: ; found: chloro-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3am) Yield 72% (96.4 mg); yellow solid, mp ; IR (KBr): 1706, 1608, 1527, 1496, 1385, 1314, 1259, 1077 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.37 (d, J = 7.8 Hz, 1H), 8.21 (s, 1H), 8.04 (d, J = 8.4 Hz, 1H), 7.87 (s, 1H), 7.76 (t, J = 7.8 Hz, 1H), 7.67 (t, J = 7.2 Hz, 1H), 6.85 (s, 1H), 3.38 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ = 167.0, 140.6, 134.4, 133.1, 131.6, 130.5, 128.9, 127.2, 126.6, 126.2, 123.7, 123.0, 119.4, 114.9, 105.9, HRMS (ESI): m/z [M + Na] + calcd for C16H10ClNONa: ; found: bromo-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3an) Yield 67% (104.6 mg); yellow solid, mp ; IR (KBr): 1723, 1703, 1604, 1495, 1384, 1314, 1260, 1079 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.38 (d, J = 7.8 Hz, 1H), 8.24 (s, 1H), 8.07 (s, 1H), 8.05 (d, J = 7.8 Hz, 1H), 7.77 (t, J = 7.2 Hz, 1H), 7.68 (t, J = 7.8 Hz, 1H), 7.01 (s, 1H), 3.39 (s, 3H), 13 C NMR (100 MHz, CDCl3): δ = 166.7, 140.5, 133.0, 131.5, 130.2, 128.9, 127.2, 126.6, 126.4, 123.6, 122.9, 122.3, 119.4, 117.9, 108.2, HRMS (ESI): m/z [M + Na] + calcd for C16H10BrNONa: ; found: chloro-4-methylnaphtho[3,2,1-cd]indol-5(4H)-one (3ao) Yield 46% (61.6 mg); yellow solid, mp ; IR (KBr): 1703, 1609, 1465, 1441, 1247, 1128, 1026 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.41 (d, J = 7.8 Hz, -S21-

22 1H), 8.22 (s, 1H), 7.99 (d, J = 7.8 Hz, 1H), 7.82 (d, J = 9.0 Hz, 1H), 7.74 (t, J = 7.2 Hz, 1H), 7.64 (t, J = 7.2 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H), 3.63 (s, 3H); NMR (150 MHz, CDCl3): δ = 167.4, 135.2, 132.7, 131.7, 131.4, 130.8, 129.3, 127.7, 127.2, 124.8, 123.7, 123.2, 122.7, 117.2, 112.4, HRMS (ESI): m/z [M + H] + calcd for C16H11ClNO: ; found: propylnaphtho[3,2,1-cd]indol-5(4H)-one (3ap) Yield 78% (101.9 mg); yellow oil; IR (KBr): 1705, 1614, 1526, 1489, 1463, 1310, 1215, 1074, 1040 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.48 (d, J = 7.8 Hz, 1H), 8.28 (s, 1H), 8.01 (d, J = 7.8 Hz, 1H), 7.95 (d, J = 8.4 Hz, 1H), 7.70 (t, J = 7.8 Hz, 1H), 7.59 (t, J = 7.2 Hz, 1H), 7.50 (t, J = 7.8 Hz, 1H), 6.90 (d, J = 7.2 Hz, 1H), 3.85 (t, J = 7.2 Hz, 2H), (m, 2H), 1.00 (t, J = 7.2 Hz, 3H). 13 C NMR (100 MHz, CDCl3): δ = 167.2, 139.4, 132.9, 131.5, 131.4, 128.6, 128.3, , , 126.2, 124.7, 123.1, 121.2, 115.5, 105.1, 41.9, 21.9, HRMS (ESI): m/z [M + Na] + calcd for C18H15NONa: ; found: (3-phenylpropyl)naphtho[3,2,1-cd]indol-5(4H)-one (3aq) Yield 76% (128.2 mg); yellow solid, mp ; IR (KBr): 1698, 1618, 1490, 1449, 1314, 1209, 1127, 1080, 1027 cm -1 ; 1 H NMR (600 MHz, CDCl3): δ = 8.54 (d, J = 8.4 Hz, 1H), 8.35 (s, 1H), 8.06 (d, J = 7.8 Hz, 1H), 8.01 (d, J = 7.8 Hz, 1H), 7.74 (t, J = 7.8 Hz, 1H), 7.63 (t, J = 7.8 Hz, 1H), 7.53 (t, J = 7.8 Hz,1H), 7.26 (d, J = 7.2 Hz, 2H), (m, 3H), 6.85 (d, J = 6.6 Hz, 1H), 3.95 (t, J = 7.2 Hz, 2H),2.74 (t, J = 7.8 Hz, 2H), (m, 2H). 13 C NMR (100 MHz, CDCl3): δ = 167.3, 140.9, 139.3, 133.1, 131.7, 131.5, 128.8, 128.5, 128.2, 128.1, 126.8, 126.4, 125.8, 124.8, 123.2, 121.4, 115.7, 105.2, 40.0, 33.2, HRMS (ESI): m/z [M + H] + calcd for C24H20NO: ; found: Reference 1. M. Jha, G. M. Shelke, A. Kumar, Eur. J. Org. Chem. 2014, K. Y. Park, B. T. Kim, J. N. Heo, Eur. J.Org. Chem. 2014, L. Cheng, L. Liu, D. Wang, Y. J. Chen, Org. Lett., 2009, 11, L. Nassar-Hardy, C. Deraedt, E. Fouquet, F. X. Felpin, Eur. J.Org. Chem. 2011, S22-

23 10. Appendix: spectral copies of 1 H NMR, and 13 C NMR (substrates 2i-2q; 4) -S23-

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35 Appendix: spectral copies of 1 H NMR, and 13 C NMR (products) -S35-

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