Supporting Information for. An Approach to Tetraphenylenes via Pd-Catalyzed C H Functionalization

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1 Supporting Information for An Approach to Tetraphenylenes via Pd-Catalyzed C H Functionalization Hang Jiang, Yu Zhang, Dushen Chen, Bo Zhou, and Yanghui Zhang * Department of Chemistry, and Shanghai Key Lab of Chemical Assessment and Sustainability, Tongji University, 1239 Siping Road, Shanghai, , P. R. China. *To whom correspondence should be addressed. zhangyanghui@tongji.edu.cn Table of Contents I. General Information S2 II. Experimental procedure for the synthesis of substrates III. General procedure for the optimization of reaction conditions IV. General procedure for Pd-catalyzed homocoupling of 2-iodobiphenyls S2 S3 S4 V. General procedure for Pd-catalyzed cross-coupling of 2-iodobiphenyls S4 VI. Oxidation of dimethyltetraphenylene VII. Pd-catalyzed coupling of 2-iodobiphenyl and iodobenzene VIII. Gram-scale synthesis of tetraphenylene IX. References S5 S6 S6 S6 X. Characterization of synthesized compounds S7 XI. NMR and GC-MS Spectra S18 S1

2 I. General Information: Pd(OAc) 2 was purchased from Strem Chemicals. All of the solvents were purified by distillation prior to use. Unless otherwise noted, the other commercial chemicals were used without further purification. and spectra were recorded on Bruker ARX400. High resolution mass spectra were measured on Bruker MicroTOF II ESI-TOF or EI-TOF (Agilent 6538 UHD) mass spectrometer. GC-MS data were tested with ThermoFisher Trace1300-ISQ (EI). Melting points were measured with a WRS-2A melting point apparatus. spectra were recorded in CDCl 3, (CD 3 ) 2 CO, or (CD 3 ) 2 SO and referenced to residual CHCl 3 at 7.26 ppm, (CH 3 ) 2 CO at 2.09 ppm, or (CH 3 ) 2 SO at 2.54 ppm, respectively. spectra are referenced to the central peak of CDCl 3 at 77.0 ppm, (CD 3 ) 2 CO at ppm, and (CD 3 ) 2 SO at ppm, respectively. Multiplicities are reported using the following abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad resonance. II. Experimental procedure for the synthesis of substrates Preparation of 3-iodo-4-aminobiphenyl (6f) 1 : 4-Aminobiphenyl (10.0 mmol, 1.69 g), iodine (10.0 mmol, 2.54 g) and NaHCO 3 (30.0 mmol, 2.52 g) were dissolved in a mixture of DCM (40 ml) and H 2 O (20 ml), and the reaction mixture was stirred at room temperature overnight. The organic layer was separated and the aqueous layer was extracted with DCM (20 ml x 3). The combined organic phases were washed with brine (20 ml x 2) and dried over anhydrous Na 2 SO 4. The filtrate was concentrated in vacuo and the crude mixture was purified by silica gel column chromatography (petroleum ether and ethyl acetate) to give the desired compound as a brown liquid (1.92 g, 65% yield). Preparation of substituted 2-aminobiphenyls (2e-11e) 2 : To a 100 ml thick-walled ground flask equipped with PTFE stopcock on side-arm were added a magnetic stir-bar, substituted 2-iodoaniline (5.0 mmol), corresponding substituted phenylboronic acid (10.0 mmol, 2.0 equiv), and K 2 CO 3 (12.5 mmol, 2.5 equiv, 1.73 g). The flask was equipped with a rubber septum and sealed up. The reaction flask was evacuated and back-filled with argon, followed by the addition of acetone (10.0 ml) and water (12.0 ml) with a gas-tight syringe. The reaction mixture was stirred and heated to 65 C. A solution of Pd(OAc) 2 (0.03 mmol, 0.6 mmol%, S2

3 6.7 mg) in acetone (2.0 ml) was then introduced to the reaction mixture with a gas-tight syringe. After the reaction mixture was stirred at 65 C overnight, it was allowed to cool to room temperature. The reaction mixture was extracted with ethyl acetate (4 x 40 ml), and the combined organic phases were washed with 50 ml of water. The organic phases were dried over anhydrous Na 2 SO 4, and concentrated in vacuo. The crude product was purified by silica gel column chromatography (petroleum ether and ethyl acetate) to give the corresponding substituted 2-aminobiphenyls (2e-11e). Preparation of 2-iodobiphenyls (1-11) 3 : 2-Aminobiphenyl (5.0 mmol) was added slowly to a stirred mixture of conc. HCl (36-38%; 6.5 mmol, 2.3 ml) and water (8.5 ml). An aqueous solution of NaNO 2 (20%; 7.5 mmol, 2.59g) was added to the reaction mixture below 5 C within 10 min and stirred for 1 h at the same temperature. An aqueous solution of KI (10.0 mmol, 1.66 g) in water (10.0 ml) was added and the reaction mixture was stirred at room temperature overnight. Ethyl acetate (50 ml) was added to the reaction mixture and the organic phase was treated with saturated NaHSO 3 to decolorize. The aqueous phase was extracted with ethyl acetate (3 x 10 ml). The combined organic phases were dried over anhydrous Na 2 SO 4 and concentrated in vacuo. The crude product was purified by silica gel column chromatography (petroleum ether) to give the desired compounds (1-11). III. General procedure for the optimization of the reaction conditions A 35 ml thick-walled tube (with a Teflon high pressure valve) equipped with a magnetic stir bar was charged with Pd(OAc) 2 followed by 2-iodobiphenyl (84.0 mg, 0.3 mmol), silver salt, additives, and TFA. The tube was placed into an oil bath preheated to 100 C. After the reaction mixture was stirred at 100 C for 12 h, it was allowed to cool to room temperature. The reaction mixture was diluted with ethyl acetate and then filtered through a small pad of Celite. The filtrate was neutralized with saturated aqueous NaHCO 3. The aqueous phase was separated and back-extracted with ethyl acetate (3 x 5 ml). The combined organic phases were dried over anhydrous Na 2 SO 4 and concentrated in vacuo. The yield was determined by analysis of crude product using Cl 2 CHCHCl 2 as the internal standard. S3

4 IV. General procedure for Pd-catalyzed homocoupling of 2-iodobiphenyls A 35 ml thick-walled tube (with a Teflon high pressure valve) equipped with a magnetic stir bar was charged with Pd(OAc) 2 followed by 2-iodobiphenyl (2-6, 10, 11) (0.3 mmol), Ag 2 CO 3 (0.15 mmol, 41.4 mg), and TFA (2.5 ml). The tube was placed into an oil bath preheated to 100 C. After the reaction mixture was stirred for a certain length of time, it was allowed to cool to room temperature. The reaction mixture was diluted with ethyl acetate and then filtered through a small pad of Celite. The filtrate was neutralized with saturated aqueous NaHCO 3. The aqueous phase was separated and back-extracted with ethyl acetate (3 x 5 ml). The combined organic phases were dried over anhydrous Na 2 SO 4 and concentrated in vacuo. The crude product was purified by silica gel preparative TLC to give the corresponding products (2a-6a, 10a or 10a ). V. General procedure for Pd-catalyzed cross-coupling of 2-iodobiphenyls A 35 ml thick-walled tube (with a Teflon high pressure valve) equipped with a magnetic stir bar was charged with Pd(OAc) 2 (0.06 mmol, 30 mol%, 13.5 mg) followed by 2-iodobiphenyl (1) (0.2 mmol), substituted 2-iodobiphenyl (5, 7-9) (0.2 mmol), Ag 2 CO 3 (0.2 mmol, 55.2 mg), and TFA (2.0 ml). The tube was placed into an oil bath preheated to 100 C. After the reaction mixture was stirred for a certain length of time, it was allowed to cool to room temperature. The reaction mixture was diluted with ethyl acetate and then filtered through a small pad of Celite. The filtrate was neutralized with saturated aqueous NaHCO 3. The aqueous phase was separated and back-extracted with ethyl acetate (3 x 5 ml). The combined organic phases were dried over anhydrous Na 2 SO 4 and concentrated in vacuo. The crude product was purified by silica gel preparative TLC to give the cross-coupled products (5c, 7c, 9c) and homo-coupled products (1, 7a + 7a. 9a + 9a, 5a). S4

5 Table S1. Pd-catalyzed cross-coupling of 2-iodobiphenyls a Isolated yield; b The isomeric ratio was determined by analysis VI. Oxidation of dimethyltetraphenylene 4 : The homocoupling of 10 or 11 formed an inseparable mixture of two isomeric products 10a and 10a. Fortunately, the isomers could be separated following oxidation to the corresponding tetraphenylene dicarboxylic acids 10d and 10d with KMnO 4. A 35 ml thick-walled tube (with a Teflon high pressure valve) equipped with a magnetic stir bar was charged with a mixture of 10a and 10a (0.12 mmol, 39.8 mg) followed by KMnO 4 (1.2 mmol, mg) and pyridine (1.0 ml) in water (1.0 ml). After it was stirred for 48 h at 180 C, the reaction mixture was allowed to cool to room temperature. The reaction mixture was diluted with ethyl acetate and then filtered through a small pad of Celite. The filtrate was acidified with 1 M aqueous HCl until ph was 2. The aqueous phase was separated and back-extracted with ethyl acetate S5

6 (10 ml). The combined organic phases were dried over anhydrous Na 2 SO 4 and concentrated in vacuo. The crude product was purified by silica gel preparative TLC to give the products (10d and 10d ) (16.3 mg and 16.6 mg, 70% overall yield). VII. Pd-catalyzed coupling of 2-iodobiphenyl and iodobenzene A 35 ml thick-walled tube (with a Teflon high pressure valve) equipped with a magnetic stir bar was charged with Pd(OAc) 2 (0.045 mmol, 15 mol%, 10.1 mg) followed by 2-iodobiphenyl (1) (0.3 mmol, 84.0 mg), iodobenzene (0.3 mmol, 61.2 mg), Ag 2 CO 3 (0.3 mmol, 82.7 mg), and TFA (2.5 ml). The tube was placed into an oil bath preheated to 100 C. After the reaction mixture was stirred for 12 h, it was allowed to cool to room temperature. The reaction mixture was diluted with ethyl acetate and then filtered through a small pad of Celite. The filtrate was neutralized with saturated aqueous NaHCO 3. The aqueous phase was separated and back-extracted with ethyl acetate (3 x 5 ml). The combined organic phases were dried over anhydrous Na 2 SO 4 and concentrated in vacuo. The crude product was purified by silica gel preparative TLC to give a mixture of triphenylene (0.024 mmol, 8% yield) and tetraphenylene (0.055 mmol, 37% yield) (The yields were determined by 1 HNMR analysis of a mixture of tetraphenylene and triphenylene). VIII. Gram-scale synthesis of tetraphenylene A 100 ml thick-walled tube (with a Teflon high pressure valve) equipped with a magnetic stir bar was charged with Pd(OAc) 2 (0.18 mmol, 5 mol %, 40.1 mg) followed by 2-iodobiphenyl (1.0 g, 3.57 mmol), Ag 2 CO 3 (1.79 mmol, 0.5 equiv, 0.49 g), and TFA (10.0 ml). The tube was placed into an oil bath preheated to 100 C. After the reaction mixture was stirred at 100 C for 6 h, it was allowed to cool to room temperature. The reaction mixture was diluted with ethyl acetate and then filtered through a small pad of Celite. The filtrate was neutralized with saturated aqueous NaHCO 3. The aqueous phase was separated and back-extracted with ethyl acetate (3 x 20 ml). The combined organic phases were dried over anhydrous Na 2 SO 4 and concentrated in vacuo. The crude product was purified by silica gel column chromatography (petroleum ether) to give the desired compound as a white solid (0.27 g, 50% yield). While using 3.0 g 2-iodobiphenyl (10.71 mmol) in TFA (30.0 ml), the yield of tetraphenylene was 48% (0.78 g). IX. References (1) Roman, D. S.; Takahashi, Y.; Charette, A. B. Org. Lett. 2011, 13, S6

7 (2) Wallow, T. I.; Novak, B. M. J. Org. Chem. 1994, 59, (3) Cho, S. Y.; Grimsdale, A. C.; Jones, D. J.; Watkins, S. E.; Holmes, A. B. J. Am. Chem. Soc. 2007, 129, (4) Hellwinkel, D.; Reiff, G.; Nykodym, V. J. Liebigs Ann. Chem. 1977, X. Characterization of synthesized compounds 2-iodobiphenyl (1) The product was prepared using the general procedure above and was isolated as a colorless liquid (1.26 g, 90% yield). (400 MHz, CDCl 3 ): δ 7.98 (dd, J = 8.0, 1.0 Hz, 1 H), (m, 4 H), (m, 3 H), 7.06 (ddd, J = 9.2, 7.4, 1.8 Hz, 1 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , The data are identical to: Cho, S. Y.; Grimsdale, A. C.; Jones, D. J.; Watkins, S. E.; Holmes, A. B. J. Am. Chem. Soc. 2007, 129, ,3 -dimethyl-2-aminobiphenyl (2e) The product was prepared using the general procedure above and was isolated as a yellow liquid (0.94 g, 95% yield). (400 MHz, CDCl 3 ): δ 7.36 (t, J = 7.5 Hz, 1 H), (m, 2 H), 7.19 (d, J = 7.4 Hz, 1 H), (m, 2 H), 6.72 (d, J = 7.8 Hz, 1 H), 3.60 (br s, 2 H), 2.43 (s, 3 H), 2.31 (s, 3 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , , , , 20.42, HRMS (ESI-TOF) m/z: calcd for C 14 H 16 N + : (M + H) +, found: The data are identical to: Racowski, J. M.; Ball, N. D.; Sanford, M. S. J. Am. Chem. Soc. 2011, 133, ,4 -dimethyl-2-aminobiphenyl (3e) The product was prepared using the general procedure above and was isolated as a yellow liquid (0.92 g, 93% yield). (400 MHz, CDCl 3 ): δ 7.39 (d, J = 7.9 Hz, 2 H), 7.29 (d, J = 7.9 Hz, 2 H), 7.07 (d, J = 7.6 Hz, 1 H), 6.70 (d, J = 7.6 Hz, 1 H), 6.64 (s, 1 H), 3.62 (br s, 2 H), 2.44 (s, 3 H), 2.36 (s, 3 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , , 21.13, HRMS (ESI-TOF) m/z: calcd for C 14 H 16 N + : S7

8 (M + H) +, found: ,4 -difluoro-2-aminobiphenyl (4e) The product was prepared using the general procedure above and was isolated as a yellow liquid (0.98 g, 96% yield). (400 MHz, CDCl 3 ): δ (m, 2 H), (m, 2 H), 7.02 (dd, J = 8.3, 6.5 Hz, 1 H), (m, 2 H), 3.82 (br s, 2 H); (100 MHz, CDCl 3 ): δ (d, J C-F = Hz), (d, J C-F = Hz), (d, J C-F = 10.9 Hz), (d, J C-F = 3.3 Hz), (d, J C-F = 9.8 Hz), (d, J C-F = 7.9 Hz), (d, J C-F = 2.7 Hz), (d, J C-F = 21.2 Hz), (d, J C-F = 21.4 Hz), (d, J C-F = 24.6 Hz). HRMS (ESI-TOF) m/z: calcd for C 12 H 10 F 2 N + : (M + H) +, found: ,4 -dichloro-2-aminobiphenyl (5e) The product was prepared using the general procedure above and was isolated as a yellow liquid (1.12 g, 94% yield). (400 MHz, CDCl 3 ): δ (m, 2 H), (m, 2 H), 6.99 (d, J = 8.0 Hz, 1 H), 6.77 (dd, J = 8.1, 2.0 Hz, 1 H), 6.74 (d, J = 2.0 Hz, 1 H), 3.78 (br s, 2 H),; (100 MHz, CDCl 3 ): δ , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 12 H 10 Cl 2 N + : (M + H) +, found: iodo-4-aminobiphenyl (6f) The product was prepared using the procedure above and was isolated as a brown liquid (1.92 g, 65% yield). (400 MHz, CDCl 3 ): δ 7.90 (d, J = 8.0 Hz, 1 H), (m, 2 H), (m, 3 H), (m, 1 H), 6.81 (d, J = 8.2 Hz, 1 H), 4.16 (br s, 2 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 12 H 11 IN + : (M + H) +, found: ,3 -diphenyl-2-aminobiphenyl (6e) S8

9 The product was prepared using the general procedure above and was isolated as a brown liquid (1.19 g, 74% yield). (400 MHz, CDCl 3 ): δ 7.88 (s, 1 H), (m, 5 H), (m, 9 H), (m, 1 H), 6.93 (d, J = 8.2 Hz, 1 H), 3.95 (br s, 2 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 24 H 20 N + : (M + H) +, found: chloro-2-aminobiphenyl (7e) The product was prepared using the general procedure above and was isolated as a yellow liquid (0.94 g, 92% yield). (400 MHz, CDCl 3 ): δ (m, 4 H), 7.20 (td, J = 7.6, 0.9 Hz, 1 H), 7.13 (d, J = 7.6 Hz, 1 H), 6.86 (t, J = 7.5 Hz, 1 H), 6.79 (d, J = 8.0 Hz, 1 H), 3.75 (br s, 2 H); 13 C NMR (100 MHz, CDCl 3 ): δ , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 12 H 11 ClN + : (M + H) +, found: The data are identical to: Felpin, F. -X.; Fouquet, E.; Zakri, C. Adv. Synth. Catal. 2009, 351, chloro-2-aminobiphenyl (8e) The product was prepared using the general procedure above and was isolated as a yellow liquid (0.92 g, 90% yield). (400 MHz, CDCl 3 ): δ (m, 4 H), (m, 1 H), 7.06 (d, J = 8.1 Hz, 1 H), 6.82 (dd, J = 8.1, 1.8 Hz, 1 H), 6.77 (d, J = 1.9 Hz, 1 H), 3.74 (br s, 2 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 12 H 11 ClN + : (M + H) +, found: methoxy-2-aminobiphenyl (9e) The product was prepared using the general procedure above and was isolated as a yellow liquid (0.82 g, 82% yield). (400 MHz, CDCl 3 ): δ 7.43 (d, J = 8.6 Hz, 2 H), (m, 2 H), 7.02 (d, J = 8.6 Hz, 2 H), 6.86 (td, J = 7.5, 0.5 Hz, 1 H), 6.79 (d, J = 7.9 Hz, 1 H), 3.88 (s, 3 H), 3.68 (br s, 2 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 13 H 14 NO + : (M + H) +, found: The data are identical to: Stokes, B. J.; Jovanovic, B.; Dong, H.; Richert, K. J.; Riell, R. D.; Driver, T. G. J. Org. Chem. 2009, 74, S9

10 3 -methyl-2-aminobiphenyl (10e) The product was prepared using the general procedure above and was isolated as a yellow liquid (0.85 g, 93% yield). (400 MHz, CDCl 3 ): δ 7.37 (t, J = 7.4 Hz, 1 H), (m, 2 H), (m, 3 H), 6.85 (t, J = 7.4 Hz, 1 H), 6.79 (d, J = 8.0 Hz, 1 H), 3.59 (br s, 2 H), 2.43 (s, 3 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 13 H 14 N + : (M + H) +, found: The data are identical to: Stokes, B. J.; Jovanovic, B.; Dong, H.; Richert, K. J.; Riell, R. D.; Driver, T. G. J. Org. Chem. 2009, 74, methyl-2-aminobiphenyl (11e) The product was prepared using the general procedure above and was isolated as a yellow liquid (0.89 g, 97% yield). (400 MHz, CDCl 3 ): δ (m, 4 H), (m, 1 H), (m, 2 H), 6.73 (d, J = 7.8 Hz, 1 H), 3.67 (br s, 2 H), 2.32 (s, 3 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 13 H 14 N + : (M + H) +, found: The data are identical to: Stokes, B. J.; Jovanovic, B.; Dong, H.; Richert, K. J.; Riell, R. D.; Driver, T. G. J. Org. Chem. 2009, 74, ,3 -dimethyl-2-iodobiphenyl (2) The product was prepared using the general procedure above and was isolated as a colorless liquid (1.23 g, 80% yield). (400 MHz, CDCl 3 ): δ 7.81 (d, J = 8.0 Hz, 1 H), 7.31 (t, J = 7.8 Hz, 1 H), 7.20 (d, J = 7.6 Hz, 1 H), (m, 3 H), 6.86 (ddd, J = 8.0, 2.3, 0.6 Hz, 1 H), 2.42 (s, 3 H), 2.33 (s, 3 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , , , 94.43, 21.45, The data are identical to: Racowski, J. M.; Ball, N. D.; Sanford, M. S. J. Am. Chem. Soc. 2011, 133, ,4 -dimethyl-2-iodobiphenyl (3) S10

11 The product was prepared using the general procedure above and was isolated as a colorless liquid (1.28 g, 83% yield). (400 MHz, (CD 3 ) 2 CO): δ 7.85 (d, J = 0.6 Hz, 1 H), (m, 3 H), (m, 3 H), 2.41 (s, 3 H), 2.38 (s, 3 H); (100 MHz, (CD 3 ) 2 CO): δ145.31, , , , , , , , , 99.58, 21.94, ,4 -difluoro-2-iodobiphenyl (4) The product was prepared using the general procedure above and was isolated as a colorless liquid (1.22 g, 77% yield). (400 MHz, CDCl 3 ): δ 7.69 (dd, J = 8.2, 2.6 Hz, 1 H), (m, 3 H), (m, 3 H); (100 MHz, CDCl 3 ): δ (d. J C-F = Hz), (d, J C-F = Hz), (d, J C-F = 3.5 Hz), (d, J C-F = 3.4 Hz), (d, J C-F = 8.1 Hz), (d, J C-F = 8.0 Hz), (d, J C-F = 23.5 Hz), (d, J C-F = 20.8 Hz), (d, J C-F = 21.4 Hz), (d, J C-F = 8.0 Hz). 4,4 -dichloro-2-iodobiphenyl (5) The product was prepared using the general procedure above and was isolated as a colorless solid (1.47 g, 84% yield). m.p C. (400 MHz, CDCl 3 ): δ 7.95 (d, J = 2.1 Hz, 1 H), (m, 2 H), 7.37 (dd, J = 8.3, 2.1 Hz, 1 H), (m, 2 H), 7.19 (d, J = 8.2 Hz, 1 H); 13 C NMR (100 MHz, CDCl 3 ): δ , , , , , , , , , ,3 -diphenyl-2-iodobiphenyl (6) The product was prepared using the general procedure above and was isolated as a colorless solid (1.51 g, 70% yield). m.p C. (400 MHz, CDCl 3 ): δ 8.04 (d, J = 8.2 Hz, 1 H), (m, 4 H), (m, 3 H), 7.54 (dd, J = 7.7, 0.5 Hz, 1 H), (m, 4 H), (m, 3 H), 7.30 (dd, J = 8.2, 2.3 Hz, 1 H). (100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , S11

12 127.41, , , , chloro-2-iodobiphenyl (7) The product was prepared using the general procedure above and was isolated as a colorless liquid (1.29 g, 82% yield). (400 MHz, CDCl 3 ): δ 7.95 (dd, J = 8.0, 0.9 Hz, 1 H), (m, 3 H), (m, 3 H), 7.04 (td, J = 7.8, 1.7 Hz, 1 H); (100 MHz, CDCl 3 ): δ , , , , , , , , 98.48, chloro-2-iodobiphenyl (8) The product was prepared using the general procedure above and was isolated as a colorless liquid (1.26 g, 80% yield). (400 MHz, CDCl 3 ): δ 7.98 (d, J = 2.1 Hz, 1 H), (m,3 H), 7.39 (dd, J = 8.2, 2.1 Hz, 1 H), (m, 2 H), 7.24 (d, J = 8.2 Hz, 1 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , methoxy-2-iodobiphenyl (9) The product was prepared using the general procedure above and was isolated as a colorless solid (1.18 g, 76% yield). m.p C. (400 MHz, CDCl 3 ): δ 7.95 (dd, J = 7.9, 0.9 Hz, 1 H), 7.76 (td, J = 7.5, 1.1 Hz, 1 H), (m, 3 H), 7.01 (td, J = 7.8, 1.8 Hz, 1 H), (m, 2 H), 3.87 (s, 3 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , 99.17, methyl-2-iodobiphenyl (10) The product was prepared using the general procedure above and was isolated as a colorless liquid (1.25 g, 85% yield). (400 MHz, CDCl 3 ): δ 7.99 (d, J = 7.9 Hz, 1 H), (m, 3 H), (m, 3 H), 7.06 (td, J = 8.1, 1.2 Hz, 1 H), 2.46 (s, 3 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , , , 98.62, methyl-2-iodobiphenyl (11) S12

13 The product was prepared using the general procedure above and was isolated as a colorless liquid (1.18 g, 80% yield). (400 MHz, CDCl 3 ): δ 7.85 (d, J = 8.0 Hz, 1 H), (m, 3 H), (m, 2 H), 7.18 (d, J = 1.7 Hz, 1 H), 6.90 (dd, J = 8.0, 1.7 Hz, 1 H), 2.37 (s, 3 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , 94.41, tetraphenylene (1a) The product was prepared using the general procedure above and was isolated as a white solid (0.3 mmol scale, 31.0 mg, 68% yield). m.p C. (400 MHz, CDCl 3 ): δ (m, 8 H), (m, 8 H); (100 MHz, CDCl 3 ): δ , , HRMS (ESI-TOF) m/z: calcd for C 24 H 16 Na + : (M + Na) +, found: The NMR data are identical to: Schaub, T.; Radius, U. Chem.-Eur. J. 2005, 11, The m.p. is close to: Cade, J. A.; Pilbeam, A. J. Chem. Soc. 1964, 114. (m.p.: C ). single crystal X-ray crystallography of 1a ORTEP drawing of 1a. Thermal ellipsoids are shown at 30% probability; hydrogen atoms are omitted for clarity. 2,7,10,15-tetramethyl-tetraphenylene (2a) The product was prepared using the general procedure above and was isolated as a white solid (0.3 S13

14 mmol scale, 38.4 mg, 71% yield). m.p C. (400 MHz, CDCl 3 ): δ (m, 8 H), 7.02 (s, 4 H), 2.35 (m, 12 H); (100 MHz, CDCl 3 ): δ , , , , , , HRMS (ESI-TOF) m/z: calcd for C 28 H 24 Na + : (M + Na) +, found: ,7,10,15-tetrafluoro-tetraphenylene (4a) The product was prepared using the general procedure above and was isolated as a white solid (0.3 mmol scale, 35.0 mg, 62% yield). m.p C. (400 MHz, CDCl 3 ): δ 7.10 (dd, J = 8.5, 5.7 Hz, 4 H), 7.00 (ddd, J = 8.4, 8.4, 2.7 Hz, 4 H), 6.87 (dd, J = 9.2, 2.7 Hz, 4 H); (100 MHz, CDCl 3 ): δ (d, J C-F = Hz), (d, J C-F = 8.0 Hz), (d, J C-F = 3.2 Hz), (d, J C-F = 8.3 Hz), (d, J C-F = 21.7 Hz), (d, J C-F = 20.9 Hz). HRMS (ESI-TOF) m/z: calcd for C 24 H 12 F 4 Na + : (M + Na) +, found: The NMR data are identical to: Li, X.; Han, J.-W.; Wong, H. N. C. Asian J. Org. Chem. 2016, 5, 74. The m.p. is close to: Li, X.; Han, J.-W.; Wong, H. N. C. Asian J. Org. Chem. 2016, 5, 74. (m.p.: C ). 2,7,10,15-tetrachloro-tetraphenylene (5a) The product was prepared using the general procedure above and was isolated as a white solid (0.1 mmol scale, 9.1 mg, 41% yield). m.p C. (400 MHz, CDCl 3 ): δ 7.30 (dd, J = 8.2, 2.2 Hz, 4 H), 7.15 (d, J = 2.1 Hz, 4 H), 7.07 (d, J = 8.2 Hz, 4 H); (100 MHz, CDCl 3 ): δ , , , , , HRMS (EI-TOF) m/z: calcd for C 24 H 12 Cl 4 : ; found: The NMR data are identical to: Li, X.; Han, J.-W.; Wong, H. N. C. Asian J. Org. Chem. 2016, 5, 74. The m.p. is close to: Li, X.; Han, J.-W.; Wong, H. N. C. Asian J. Org. Chem. 2016, 5, 74. (m.p C ). 2,7,10,15-tetraphenyl-tetraphenylene (6a) S14

15 The product was prepared using the general procedure above and was isolated as a white solid (0.1 mmol scale, 17.0 mg, 56% yield). Decomposed ~262.0 C. (400 MHz, CDCl 3 ): δ (m, 8 H), 7.59 (dd, J = 8.0, 1.9 Hz, 4 H), 7.53 (d, J = 1.8 Hz, 4 H), 7.41 (t, J = 7.7 Hz, 8 H), (m, 8 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 48 H 32 Na + : (M + Na) +, found: ,7-dichloro-tetraphenylene (5c) The product was prepared using the general procedure above and was isolated as a white solid (0.2 mmol scale, 18.7 mg, 25% yield). m.p C. (400 MHz, CDCl 3 ): δ (m, 4 H), 7.24 (dd, J = 8.2, 2.2 Hz, 2 H), (m, 6 H), 7.06 (d, J = 8.2 Hz, 2 H); (100 MHz, CDCl 3 ): δ , , , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 24 H 14 Cl 2 Na + : (M + Na) +, found: chloro-tetraphenylene (7c) The product was prepared using the general procedure above and was isolated as a white solid (0.2 mmol scale, 15.6 mg, 23% yield). m.p C. (400 MHz, (CD 3 ) 2 CO): δ (m, 7 H), (m, 8 H); (100 MHz, (CD 3 ) 2 CO): δ , , , , , , , , , , , , , , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 24 H 15 ClNa + : (M + Na) +, found: methoxy-tetraphenylene (9c) The product was prepared using the general procedure above and was isolated as a white solid (0.2 mmol scale, 16.0 mg, 24% yield). m.p C. (400 MHz, CDCl 3 ): δ (m, 6 H), (m, 6 H), 7.07 (d, J = 8.4 Hz, 1 H), 6.82 (dd, J = 8.4, 2.7 Hz, 1 H), 6.70 (d, J = 2.6 Hz, 1 H), 3.77 (s, 3 H); (100 MHz, CDCl 3 ): δ , , , , , S15

16 141.46, , , , , , , , , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 25 H 18 NaO + : (M + Na) +, found: , 10-dimethyl-tetraphenylene (10a) and 2, 7-dimethyl-tetraphenylene (10a ) The products were prepared using the general procedure above and were isolated as a white solid (0.3 mmol scale, 29.9 mg, 60% overall yield). HRMS (ESI-TOF) m/z: calcd for C 26 H 20 Na + : (M + Na) +, found: , 10-dimethyl-tetraphenylene (10a) and 2, 7-dimethyl-tetraphenylene (10a ) The products were prepared using the general procedure above and were isolated as a white solid (0.3 mmol scale, 27.9 mg, 56% overall yield). HRMS (ESI-TOF) m/z: calcd for C 26 H 20 Na + : (M + Na) +, found: , 10-dicarboxy-tetraphenylene (10d) or 2, 7-dicarboxy-tetraphenylene (10d ) The product was prepared using the procedure above and was isolated as a white solid (16.3 mg, 34.7% yield). (400 MHz, (CD 3 ) 2 CO): δ 8.06 (dd, J = 8.0, 1.7 Hz, 2 H), 7.87 (d, J = 1.6 Hz, 2 H), (m, 6 H), (m, 4 H); (100 MHz, (CD 3 ) 2 CO): δ , , , , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 26 H 16 NaO + 4 : (M + Na) +, found: , 7-dicarboxy-tetraphenylene (10d ) or 2, 10-dicarboxy-tetraphenylene (10d) The product was prepared using the procedure above and was isolated as a white solid (16.6 mg, S16

17 35.3% yield). (400 MHz, (CD 3 ) 2 SO): δ 7.93 (dd, J = 7.9, 1.5 Hz, 2 H), 7.69 (d, J = 1.2 Hz, 2 H), (m, 4 H), 7.35 (d, J = 8.0 Hz, 2 H), (m, 4 H); (100 MHz, (CD 3 ) 2 SO): δ , , , , , , , , , , , , HRMS (ESI-TOF) m/z: calcd for C 26 H 16 NaO + 4 : (M + Na) +, found: triphenylene The product was prepared using the procedure above and was isolated as a white solid along with tetraphenylene. (400 MHz, CDCl 3 ): δ (m, 6 H), (m, 6 H); (100 MHz, CDCl 3 ): δ , , The data are identical to: Hsieh, J. -C.; Cheng, C. -H. Chem. Commun. 2008, 44, S17

18 XI. NMR and GC-MS Spectra 2-iodobiphenyl (1) S18

19 5,3 -dimethyl-2-aminobiphenyl (2e) S19

20 4,4 -dimethyl-2-aminobiphenyl (3e) S20

21 4,4 -difluoro-2-aminobiphenyl (4e) S21

22 4,4 -dichloro-2-aminobiphenyl (5e) S22

23 3-iodo-4-aminobiphenyl (6f) S23

24 5,3 -diphenyl-2-aminobiphenyl (6e) S24

25 4 -chloro-2-aminobiphenyl (7e) S25

26 4-chloro-2-aminobiphenyl (8e) S26

27 4 -methoxy-2-aminobiphenyl (9e) S27

28 3 -methyl-2-aminobiphenyl (10e) S28

29 5-methyl-2-aminobiphenyl (11e) S29

30 5,3 -dimethyl-2-iodobiphenyl (2) S30

31 4,4 -dimethyl-2-iodobiphenyl (3) S31

32 4,4 -difluoro-2-iodobiphenyl (4) S32

33 4,4 -dichloro-2-iodobiphenyl (5) S33

34 5,3 -diphenyl-2-iodobiphenyl (6) S34

35 4 -chloro-2-iodobiphenyl (7) S35

36 4-chloro-2-iodobiphenyl (8) S36

37 4 -methoxy-2-iodobiphenyl (9) S37

38 3 -methyl-2-iodobiphenyl (10) S38

39 5-methyl-2-iodobiphenyl (11) S39

40 tetraphenylene (1a) S40

41 2,7,10,15-tetramethyl-tetraphenylene (2a) S41

42 2,7,10,15-tetrafluoro-tetraphenylene (4a) S42

43 2,7,10,15-tetrachloro-tetraphenylene (5a) S43

44 2,7,10,15-tetraphenyl-tetraphenylene (6a) S44

45 2,7-dichloro-tetraphenylene (5c) S45

46 2-chloro-tetraphenylene (7c) S46

47 2-methoxy-tetraphenylene (9c) S47

48 Relative Abundance Relative Abundance Relative Abundance 2, 10-dichloro-tetraphenylene (7a) and 2, 7-dichloro-tetraphenylene (7a ) GC-MS F:\DATA\JH\DATA\JH-N-2 7/29/2014 8:58:27 PM RT: RT: MA: NL: 2.12E8 TIC MS JH-N Time (min) RT: RT: MA: NL: 2.12E8 TIC MS JH-N Time (min) JH-N-2 #3587 RT: AV: 1 SB: , NL: 2.57E7 T: {0,0} + c EI Full ms [ ] m/z S48

49 Relative Abundance Relative Abundance Relative Abundance 2, 10-dichloro-tetraphenylene (7a) and 2, 7-dichloro-tetraphenylene (7a ) GC-MS F:\DATA\JH\DATA\JH-J-2 7/27/2014 2:34:23 AM RT: RT: MA: NL: 1.88E8 TIC MS JH-J RT: RT: AA: AA: Time (min) RT: RT: MA: NL: 1.88E8 TIC MS JH-J RT: AA: Time (min) RT: AA: JH-J-2 #3585 RT: AV: 1 SB: , NL: 2.26E7 T: {0,0} + c EI Full ms [ ] m/z S49

50 2, 10-dimethoxy-tetraphenylene (9a) and 2, 7-dimethoxy-tetraphenylene (9a ) S50

51 2, 10-dimethyl-tetraphenylene (10a) and 2, 7-dimethyl-tetraphenylene (10a ) S51

52 2, 10-dicarboxy-tetraphenylene (10d) or 2, 7-dicarboxy-tetraphenylene (10d ) S52

53 2, 7-dicarboxy-tetraphenylene (10d ) or 2, 10-dicarboxy-tetraphenylene (10d) S53

54 triphenylene and tetraphenylene S54

55 Relative Abundance Relative Abundance Relative Abundance GC-MS F:\DATA\JH\DATA\JH-TRITETRA-2 4/7/2015 6:18:08 PM RT: NL: 6.37E8 TIC MS JH- TRITETRA Time (min) JH-TRITETRA-2 #3145 RT: AV: 1 NL: 1.03E8 T: {0,0} + c EI Full ms [ ] m/z JH-TRITETRA-2 #3197 RT: AV: 1 NL: 1.27E7 T: {0,0} + c EI Full ms [ ] m/z S55