Supporting Information. Contents

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1 Supporting Information Rhodium-Catalyzed Selective Mono- and Di-Amination of Arenes with Single Directing Site On Water Md Ashif Ali,, Xiayin Yao,, Guigen Li, and Hongjian Lu, * Contents Schemes S1-S9...2 General Methods... 3 General Procedure for the Preparation of Starting Materials... 4 General Procedure for the Rh-Catalyzed Amidation with Azides Spectroscopic Data of Compounds Obtained in this Study (Schemes 2-3) General Procedure for the diamination Spectroscopic Data of Compounds Obtained in diamination (Scheme 4)...32 One-pot reaction Reactivity Study of Mono-amination (Schemes S1-S4) Preliminary Mechanistic Study (Scheme 5 and Scheme S5) Kinetic Experiments (Schemes S6-S9)...39 References Spectra

2 Schemes S1-S9 2

3 General Methods Unless otherwise stated, all commercial reagents and solvents were used without additional purification. Analytical thin layer chromatography (TLC) was performed on pre-coated silica gel GF254 plates. Visualization on TLC was achieved by the use of UV light (254 nm). Column chromatography was undertaken on silica gel ( mesh) using a proper eluent. 1 H NMR was recorded on FT AM 400 (400 MHz). Chemical shifts were quoted in parts per million (ppm) referenced to the appropriate solvent peak. The following abbreviations were used to describe peak splitting patterns when appropriate: br = broad, s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublet, td = triplet of doublet, ddd = doublet of doublet of doublet, m = multiplet. Coupling constants, J, were reported in hertz (Hz). 13 C NMR was recorded on FT AM 400 (100 MHz) and was fully decoupled by broad band proton decoupling. Chemical shifts were reported in ppm referenced to the appropriate solvent peak. Infrared (IR) spectra were recorded neat in 0.5 mm path length using a KBr. Frequencies are given in reciprocal centimeters (cm-1) and only selected absorbance is reported. High resolution mass spectra were obtained from the UHD Accurate-Mass Q-TOF. 3

4 General Procedure for the Preparation of Starting Materials Arylpyridines General procedure for the preparation of arylpyridines 1a-1k [2] Aryl pyridines were prepared according to reference [2]. A mixture of heteroaryl bromide (2.0 mmol), arylboronic acid (3.0 mmol), Pd(OAc) 2 (1.5 mol %), K 3 PO 4 7H 2 O (4.0 mmol) in mixture of isopropanol (10 ml) and water (10 ml) was stirred at 80 C for indicated time. The mixture was added to brine (40 ml) and extracted four times with ethyl acetate (25 ml x 4), the solvent was evaporated in 4

5 vacuo and the product was isolated by short column chromatography. A mixture of 3-(pyridin-2-yl)phenol (119.8 mg, 0.7 mmol), 4-methylbenzenesulfonyl chloride (267.0 mg, 1.4 mmol) and K 2 CO 3 (193.5 mg, 1.4 mmol) in CH 3 CN (8 ml) were refluxed at 125 C for 40 h. The mixture was washed by water and extracted with dichloromethane. The solvent was evaporated in vacuo and the crude reaction mixture was purified by chromatography on silica gel (4:1 n-hexane/etoac) as an eluent to give the 79.7 mg (0.25 mmol) brown oil. Yield 35%, R f = 0.3 (4:1 n-hexane/etoac); 1 H NMR (400 MHz, CDCl 3 ) δ 8.65 (d, J = 4.2 Hz, 1H), 7.90 (d, J = 7.9 Hz, 1H), (m, 3H), (m, 1H), 7.59 (d, J = 8.0 Hz, 1H), 7.36 (t, J = 8.0 Hz, 1H), 7.30 (d, J = 8.1 Hz, 2H), 7.23 (ddd, J = 7.4, 4.9, 0.8 Hz, 1H), 6.98 (dd, J = 8.1, 1.6 Hz, 1H), 2.42 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , 21.63; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 15 NO 3 S, , found A solution of 3-(pyridin-2-yl)phenol (87.3 mg, 0.51 mmol) in 2 ml of dichloromethane was prepared. To this solution was added pyridine (87.0 mg, 1.1 mmol) and the solution was cooled in an ice-salt bath. To this solution was added a solution of trifluoromethanesulfonic anhydride (437.3 mg, 1.55 mmol) in 3 ml of dichloromethane drop wise. The reaction was allowed to warm slowly and was complete after 2 hours. Water and dichloromethane were added and the layers were separated. The aqueous layer was extracted with dichloromethane. The organic extracts were dried over magnesium sulfate, filtered and evaporated to a residue. The 5

6 residue was purified by silica gel column chromatography (5:1 n-hexane/etoac) and mg (0.43 mmol) of a clear liquid (85% yield) was obtained. R f = 0.33 (3:1 n-hexane/etoac); 1 H NMR (400 MHz, CDCl 3 ) δ 8.70 (d, J = 4.5 Hz, 1H), (m, 2H), 7.77 (td, J = 7.7, 1.7 Hz, 1H), 7.71 (d, J = 7.9 Hz, 1H), 7.53 (t, J = 8.2 Hz, 1H), (m, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , (q, J = Hz); HRMS (ESI) ([M+H] + ) calcd. for C 12 H 8 F 3 NO 3 S, , found (3-((tert-butyldimethylsilyl)oxy)phenyl)pyridine was synthesize as reference [1d] : 3-(pyridin-2-yl)phenol 3 (171.2 mg, 1.0 mmol) with tert-butyldimethylchlorosilane (226.1 mg, 1.5 mmol) and imidazole (129.4 mg, 1.9 mmol) in CH 2 Cl 2 (5 ml) were stirred for 24 h. Silica gel chromatography (eluent:hexane/etoac = 30/1) of the crude product afforded the title compound as colorless oil (142.8 mg, 0.5 mmol 50%). R f = 0.50 (hexane/etoac = 5/1). The starting material 1k was prepared according to general procedure. Yield 96% (359.4 mg, 1.92 mmol), yellow oil, R f = 0.46 (hexane). 1 H NMR (400 MHz, CDCl 3 ) δ 8.54 (d, J = 2.9 Hz, 1H), 7.79 (s, 1H), (m, 2H), 7.43 (td, J = 8.4, 2.9 Hz, 1H), 7.36 (t, J = 7.6 Hz, 1H), 7.23 (d, J = 7.5 Hz, 1H), 2.44 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ (d, J = 254.3), (d, J = 3.9 Hz), , ,

7 (d, J = 23.5 Hz), , , , , (d, J = 18.5 Hz), (d, J = 4.2 Hz), Procedure for the Preparation of 2-phenylpyrimidine 1l [1h] A mixture of 2-chloropyrimidine (229.0 mg, 2.0 mmol), phenylboronic acid (365.7 mg, 3.0 mmol), Pd(OAc) 2 (3.4 mg, 1.5 mol %), K 3 PO 4 7H 2 O (1.35 g, 4.0 mmol) in mixture of isopropanol (10 ml) and water (10 ml) was stirred at 80 C for indicated time. The mixture was added to brine (40 ml) and extracted four times with ethyl acetate (25 ml x 4), the solvent was evaporated in vacuo and the crude product was purfied by short column chromatography to form desired product mg (1.6 mmol, 80%) Procedure for the Preparation of (E)-1-phenylethan-1-one O-methyl oxime 1m [1i] To a solution of acetophenone (0.61 g, 5 mmol) in ethanol (10 ml), and H 2 O (25 ml) was added NaOAc (2.72 g, 20 mmol) followed by methoxyamine hydrochloride (1.25 g, 15 mmol) under air. The reaction mixture was stirred in a pre-heated oil bath at 80 o C for 12 h and then cooled to room temperature. To the reaction mixture H 2 O (10 ml) was added, extracted by EtOAc for three times, dried over MgSO 4 and evaporated in vacuum to afford the product (0.495 g, 3.3 mmol, 66%) without any further purification. Preparation of 6-aryl substituted purine derivative 1n [1j-k] 7

8 Procedure for Step I In an oven dried round bottom flask (25 ml), free hydroxyl starting material (143.4 mg, 0.5 mmol) was taken and then dry acetonitrile (7 ml) was added followed by acetic anhydride (255.2 mg, 2.5 mmol), triethyl amine (347 μl, 2.5 mmol) and 4-dimethylaminopyridine (6.1 mg, 0.05 mmol) were added respectively and stirred for 16 h at room temperature. Then methanol (1 ml) was added stirred for additional 1 h. The solvent was evaporated under reduced pressure and crude was purified by silica gel column using hexane and ethyl acetate as eluent to form desired 207 mg (0.5 mmol, 100%). Procedure for Step II The product obtained from Step I was transferred to a oven dried Schlenk tube followed by phenylboronic acid (121.9 mg, 1.0 mmol), K 2 CO 3 (103.7 mg, 0.75 mmol) and Pd(PPh 3 ) 4 (57.8 mg, 5 mol %) were added and refilled with nitrogen gas. Then toluene (5 ml) was added crewed with Teflon cap and stirred on a preheated oil bath for 10 h. After cooling to room temperature, the mixture was transferred into a round bottom flask and solvent was evaporated under reduced pressure and crude was purified by silica gel column using hexane and ethyl acetate as eluent. (2R,3S,4S,5R)-2-(acetoxymethyl)-5-(6-phenyl-9H-purin-9-yl)tetrahydrofuran-3,4- diyl diacetate 1n: Yield 79% (0.4 mmol, mg) colorless gummy, R f = 0.48 (hexane/etoac = 5/1). 1 H NMR (400 MHz, CDCl 3 ) δ 9.03 (s, 1H), 8.75 (dd, J = 7.9, 1.6 Hz, 2H), 8.28 (s, 1H), 7.56 (q, J = 6.3 Hz, 3H), 6.30 (d, J = 5.3 Hz, 1H), 6.02 (t, J = 5.4 Hz, 1H), (m, 1H), (m, 2H), 4.40 (dd, J = 12.9, 5.1 Hz, 1H), 2.16 (s, 3H), 2.14 (s, 3H), 2.09 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , 86.38, 80.39, 73.08, 70.65, 63.05, 21.54, 20.75, 20.53,

9 Aryl Azides General Procedure for the Preparation of Aryl Azides In a 20 ml scintillation vial, aromatic amines (2.0 mmol, 1.0 equiv) was dissolved in 15 ml of HOAc and 8 ml of H 2 O and chilled in an ice bath. NaNO 2 (207.0 mg, 3.0 mmol, 1.5 equiv) was added slowly, and the resulting mixture was stirred at 0 C for one hour. NaN 3 (208.0 mg, 3.2 mmol, 1.6 equiv) was then added slowly, and the resulting mixture was warmed to ambient temperature, and stirred for 1 hour. The solution was diluted with 30 ml of water and 30 ml of CH 2 Cl 2 and basified by the slow addition of K 2 CO 3 until bubbling ceased. The phases were separated and the aqueous phase was extracted with an additional 3 20 ml of CH 2 Cl 2. The combined organic phases were washed with water (25 ml x 4) and brine (25 ml x 1). The 9

10 resulting organic phase was dried over Na 2 SO 4 and filtered. The filtrate was concentrated in vacuum and purified by column chromatography. The compound was prepared following the general procedure. Yield 90% (503.1 mg, 1.8 mmol), brown oil, R f = 0.9 (hexane/etoac = 40/1). 1 H NMR (400 MHz, CDCl 3 ) δ 7.77 (d, J = 2.3 Hz, 1H), 7.36 (dd, J = 8.6, 2.3 Hz, 1H), 7.05 (d, J = 8.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , The compound was prepared following the general procedure. Yield 95% (704.5 mg, 1.9 mmol, 95% purity), yellow solid, R f = 0.78 (hexane/etoac = 5/1). 1 H NMR (400 MHz, CDCl 3 ) δ 8.06 (d, J = 1.9 Hz, 1H), 7.63 (dd, J = 8.4, 1.9 Hz, 1H), 6.85 (d, J = 8.4 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ , , , , 88.97, In a 20 ml scintillation vial, 2,6-dibromo-4-methylaniline (208.0 mg, 2.0 mmol, 1.0 equiv) was dissolved in 15 ml of HOAc and 8 ml of H 2 O and chilled in an ice bath. NaNO 2 (207.0 mg, 3.0 mmol, 1.5 equiv) was added slowly, and the resulting mixture was stirred at 0 C for one hour. NaN 3 (208.0 mg, 3.2 mmol, 1.6 equiv) was then added slowly, and the resulting mixture was warmed to ambient temperature, and stirred for 1 hour. The solution was diluted with 30 ml of water and 30 ml of CH 2 Cl 2 10

11 and basified by the slow addition of K 2 CO 3 until bubbling ceased. The phases were separated and the aqueous phase was extracted with an additional 3 20 ml of CH 2 Cl 2. The combined organic phases were washed with water (25 ml x 4) and brine (25 ml x 1). The resulting organic phase and dried over Na 2 SO 4 and filtered. The filtrate was concentrated in vacuo and purified by column chromatography. Yield 90% (523.7 mg, 1.8 mmol), R f = 0.52 (100:1 n-hexane/etoac); 1 H NMR (400 MHz, CDCl 3 ) δ 7.29 (d, J = 0.6 Hz, 2H), 2.27 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , 20.17; HRMS (ESI) ([M+H] + ) calcd. for C 7 H 5 Br 2 N 3, , found General Procedure for the Rh-Catalyzed Amidation with Azides To a Schlenk tube equipped with a teflon plug valve and stirbar was added chelating group-containing arenes (1, 0.15 mmol), aryl azides (2, 0.15 mmol), [RhCp*Cl 2 ] 2 (3.7 mg, 4 mol %), NaBARF (5.3 mg, 4 mol %) and H 2 O (1 ml) under atmospheric conditions. The reaction mixture was vigorously stirred on a pre-heated oil bath at 110 o C for 24 h. The reaction was cooled to room temperature, diluted with CH 2 Cl 2 (10 ml) and then washed by water (5 ml x 3).The aqueous layer was extracted by CH 2 Cl 2 (5 ml x 3). The solvents were removed under reduced pressure and the crude reaction mixture was purified by chromatography on silica gel (n-hexane/etoac) as an eluent to give the desired product. 11

12 Characterization Data N-(4-nitrophenyl)-2-(pyridin-2-yl)aniline (3a): Yield 99% (43.3 mg), purified by chromatography on silica gel (5:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.23 (5:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.66 (d, J = 4.7 Hz, 1H), 8.11 (d, J = 9.1 Hz, 2H), 7.83 (dd, J = 11.1, 4.5 Hz, 1H), 7.72 (d, J = 8.1 Hz, 1H), 7.67 (d, J = 7.8 Hz, 1H), 7.60 (d, J = 8.2 Hz, 1H), 7.38 (t, J = 7.7 Hz, 1H), 7.28 (dd, J = 7.4, 5.6 Hz, 1H), 7.15 (t, J = 7.6 Hz, 1H), 7.10 (d, J = 9.1 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , ; IR (KBr) v 3450, 3005, 1580, 1500, 1474, 1275, 1260 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 17 H 13 N 3 O 2, , found Ethyl 4-((2-(pyridin-2-yl)phenyl)amino)benzoate (3b): Yield 93% (44.4 mg), purified by chromatography on silica gel (10:1-5:1 Hexanes/EtOAc), orange solid, TLC R f = 0.20 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.65 (d, J = 4.8 Hz, 1H), 7.94 (d, J = 8.6 Hz, 2H), (m, 1H), 7.69 (d, J = 8.1 Hz, 1H), 7.62 (dd, J = 13.1, 8.0 Hz, 2H), 7.33 (t, J = 7.7 Hz, 1H), 7.23 (dd, J = 6.8, 5.5 Hz, 1H), 7.16 (d, J = 8.6 Hz, 2H), 7.05 (t, J = 7.5 Hz, 1H), 4.35 (q, J = 7.1 Hz, 2H), 1.38 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, 12

13 CDCl 3 ) δ , , , , , , , , , , , , , , , , 60.37, 14.41; IR (KBr) v 3248, 3060, 1704, 1586, 1390, 1365, 1022 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 20 H 18 N 2 O 2, , found N-butyl-4-((2-(pyridin-2-yl)phenyl)amino)benzamide (3c): Yield 92% (47.7 mg) (48h), purified by chromatography on silica gel (5:1 Hexanes/EtOAc), orange oil, TLC R f = 0.21 (5:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.65 (d, J = 4.8 Hz, 1H), 7.80 (t, J = 7.8 Hz, 1H), (m, 4H), 7.55 (d, J = 8.2 Hz, 1H), 7.31 (t, J = 7.7 Hz, 1H), (m, 1H), 7.16 (d, J = 8.4 Hz, 2H), 7.02 (t, J = 7.5 Hz, 1H), 6.03 (s, 1H), 3.43 (dd, J = 13.2, 6.7 Hz, 2H), (m, 2H), 1.40 (dq, J = 14.4, 7.3 Hz, 2H), 0.95 (t, J = 7.3 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , 39.65, 31.86, 20.16, 13.79; IR (KBr) v 3284, 2307, 1785, 1586, 1546, 1425, 1281, 1153 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 22 H 23 N 3 O, , found Phenyl(2-((2-(pyridin-2-yl)phenyl)amino)phenyl)methanone (3d): Yield 90% (47.3 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.22 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.88 (d, J = 4.7 Hz, 1H), (m, 3H),

14 7.59 (m, 3H), 7.53 (t, J = 7.3 Hz, 1H), 7.45 (dd, J = 7.7, 4.3 Hz, 4H), (m, 2H), (m, 1H), 7.11 (t, J = 7.5 Hz, 1H), 6.73 (t, J = 7.5 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , , ; IR (KBr) v 3237, 3005, 1637, 1577, 1474, 1316, 1157, 937 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 24 H 18 N 2 O, , found Bromo-N-(2-(pyridin-2-yl)phenyl)aniline (3e): Yield 93% (45.4 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), orange oil, TLC R f = 0.41 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.71 (d, J = 4.2 Hz, 1H), 7.79 (td, J = 7.8, 1.8 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.65 (dd, J = 7.8, 1.3 Hz, 1H), (m, 2H), 7.43 (dd, J = 8.2, 1.2 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 6.73 (td, J = 8.0, 1.4 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , ; IR (KBr) v 3210, 3060, 1582, 1519, 1224, 1156, 1119, 1044 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 17 H 13 BrN 2, , found Ethyl 3-bromo-4-((2-(pyridin-2-yl)phenyl)amino)benzoate (3f): 14

15 Yield 96% (57.2 mg), purified by chromatography on silica gel (5:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.56 (4:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.71 (d, J = 4.8 Hz, 1H), 8.21 (d, J = 1.9 Hz, 1H), (m, 2H), 7.68 (t, J = 8.5 Hz, 2H), 7.59 (d, J = 8.2 Hz, 1H), 7.36 (dd, J = 11.0, 4.9 Hz, 2H), 7.25 (dd, J = 7.9, 4.4 Hz, 1H), 7.13 (t, J = 7.5 Hz, 1H), 4.33 (q, J = 7.1 Hz, 2H), 1.37 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , 60.67, 14.37; IR (KBr) v 3210, 3004, 1707, 1608, 1584, 1394, 1109 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 20 H 17 BrN 2 O 2, , found Chloro-2-iodo-N-(2-(pyridin-2-yl)phenyl)aniline (3g): Yield 93% (56.7 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), white solid, TLC R f = 0.50 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.71 (ddd, J = 4.9, 1.8, 0.9 Hz, 1H), (m, 1H), 7.76 (d, J = 2.4 Hz, 1H), 7.72 (d, J = 8.1 Hz, 1H), 7.67 (dd, J = 7.8, 1.5 Hz, 1H), 7.40 (dd, J = 8.3, 1.0 Hz, 1H), (m, 1H), (m, 2H), 7.14 (dd, J = 8.8, 2.4 Hz, 1H), 7.02 (td, J = 7.8, 1.2 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , 89.57; IR (KBr) v 3256, 3059, 1585, 1561, 1475, 1419, 1380, 1100 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 17 H 12 ClIN 2, , found ,4-Diiodo-N-(2-(pyridin-2-yl)phenyl)aniline (3h): 15

16 Yield 87% (65.0 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), black solid, TLC R f = 0.56 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.71 (d, J = 4.8 Hz, 1H), 8.05 (d, J = 2.0 Hz, 1H), 7.80 (td, J = 7.8, 1.8 Hz, 1H), 7.71 (d, J = 8.1 Hz, 1H), 7.66 (dd, J = 7.8, 1.3 Hz, 1H), (m, 2H), (td, J = 7.8,1.4 Hz, 1H), (m, 1H), 7.09 (d, J = 8.7 Hz, 1H), (td, J = 7.8,0.9 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , 90.45, 81.77; IR (KBr) v 3277, 3057, 1654, 1584, 1546, 1419, 1263, 1079 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 17 H 12 I 2 N 2, , found ,6-Dibromo-4-methyl-N-(2-(pyridin-2-yl)phenyl)aniline (3i): Yield 91% (57.1 mg) (48h), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), white solid, TLC R f = 0.36 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.64 (dt, J = 4.9, 1.4 Hz, 1H), (m, 2H), 7.67 (dd, J = 7.8, 1.4 Hz, 1H), 7.45 (s, 2H), (m, 2H), (m, 1H), 6.45 (d, J = 8.2 Hz, 1H), 2.34 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , 20.31; IR (KBr) v 3208, 3059, 1583, 1537, 1447, 1381, 1287, 1188 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 14 Br 2 N 2, , found

17 1-((2-(Pyridin-2-yl)phenyl)amino)anthracene-9,10-dione (3j): Yield 98% (55.3 mg), purified by chromatography on silica gel (dichloromethane), red solid, TLC R f = 0.6 (dichloromethane); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.84 (ddd, J = 4.9, 1.7, 0.9 Hz, 1H), 8.36 (dd, J = 7.7, 1.0 Hz, 1H), 8.24 (dd, J = 7.6, 1.1 Hz, 1H), 7.78 (td, J = 7.5, 1.5 Hz, 1H), (m, 4H), (m, 2H), 7.50 (dd, J = 8.7, 1.1 Hz, 1H), (m, 2H), 7.28 (td, J = 7.6, 1.2 Hz, 1H), 7.21 (ddd, J = 7.5, 4.9, 1.1 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , , , , , ; IR (KBr) v 3216, 3063, 1735, 1635, 1584, 1426, 1354, 1174 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 25 H 16 N 2 O 2, , found N-phenyl-2-(pyridin-2-yl)aniline (3k): Yield 90% (33.3 mg) (48h), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.45 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), (d, J = 4.9 Hz, 1H), (m, 1H), 7.72 (d, J = 8.1 Hz, 1H), 7.63 (dd, J = 7.8, 1.4 Hz, 1H), 7.50 (d, J = 8.3 Hz, 1H), 7.29 (td, J = 8.0, 1.5 Hz, 3H), (m, 3H), (m, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , ; IR (KBr) v 3446, 3046, 1587, 17

18 1579, 1449, 1417, 1318, 1278, 694 cm -1 ; HRMS (ESI) ([M+H] + ) calcd.for C 17 H 14 N 2, , found N-(4-methoxyphenyl)-2-(pyridin-2-yl)aniline (3l): Yield 33% (13.7 mg), purified by chromatography on silica gel (15:1 Hexanes/EtOAc), brown solid, TLC R f = 0.41 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.62 (ddd, J = 4.9, 1.7, 0.9 Hz, 1H), (m, 2H), 7.61 (d, J = 7.8 Hz, 1H), (m, 5H), (m, 3H), 3.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , IR (KBr) v 3260, 2836, 1587, 1560, 1474, 1263, 1038 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 16 N 2 O, , found N-(2-(pyridin-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (3m): Yield 38% (18.4 mg), purified by chromatography on silica gel (20:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.59 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.68 (d, J = 4.8 Hz, 1H), 7.83 (t, J = 7.7 Hz, 1H), 7.76 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 7.8 Hz, 1H), (m, 5H), 7.44 (t, J = 7.6 Hz, 18

19 2H), (m, 5H), 6.99 (t, J = 7.5 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , ; IR (KBr) v 3473, 2919, 1631, 1586, 1523, 1475, 1438, 1324 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 23 H 18 N 2, , found Methoxy-N-(2-(pyridin-2-yl)phenyl)-[1,1'-biphenyl]-2-amine (3n): Yield 81% (42.8 mg) (48h), purified by chromatography on silica gel (10:1Hexanes/EtOAc), orange oil, TLC R f = 0.32 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.08 (d, J = 4.8 Hz, 1H), (m, 1H), 7.62 (d, J = 8.1 Hz, 1H), 7.54 (dd, J = 7.8, 1.4 Hz, 1H), (m, 2H), (m, 5H), (m, 1H), 7.05 (ddd, J = 7.1, 4.9, 1.0 Hz, 1H), 6.90 (d, J = 2.9 Hz, 1H), 6.87 (dd, J = 8.7, 3.0 Hz, 1H), (m, 1H), 3.83 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , , 55.65; IR (KBr) v 3232, 3056, 1586, 1475, 1420, 1269, 1093, 1018 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 24 H 20 N 2 O, , found Bromo-4-methoxy-N-(2-(pyridin-2-yl)phenyl)aniline (3o): 19

20 Yield 91% (48.5 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.48 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.67 (d, J = 4.6 Hz, 1H), 7.78 (t, J = 7.7 Hz, 1H), 7.73 (d, J = 8.0 Hz, 1H), 7.65 (d, J = 7.8 Hz, 1H), 7.35 (d, J = 8.9 Hz, 1H), (m, 3H), 7.17 (d, J = 2.7 Hz, 1H), 6.92 (dt, J = 8.0, 4.1 Hz, 1H), 6.81 (dd, J = 8.9, 2.7 Hz, 1H), 3.78 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , 55.81; IR (KBr) v 3440, 2849, 1585, 1513, 1441, 1207, 1028 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 15 BrN 2 O, , found Methyl-N-(2-(pyridin-2-yl)phenyl)aniline (3p): Yield 91% (35.5 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.48 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.64 (dd, J = 4.1, 0.8 Hz, 1H), (m, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.66 (dd, J = 7.8, 1.2 Hz, 1H), 7.40 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 8.3 Hz, 1H), (m, 3H), 7.15 (t, J = 7.7 Hz, 1H), 6.93 (t, J = 7.5 Hz, 2H), 2.39 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , 18.30; IR (KBr) v 3250, 3052, 1676, 1586, 1560, 1420, 1379, 1241, 1093 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 16 N 2, , found

21 2-Ethyl-N-(2-(pyridin-2-yl)phenyl)aniline (3q): Yield 88% (36.2 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), orange oil, TLC R f = 0.4 (5:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.63 (d, J = 4.9 Hz, 1H), (m, 2H), 7.66 (dd, J = 7.8, 1.5 Hz, 1H), 7.41 (dd, J = 8.0, 1.1 Hz, 1H), 7.33 (dd, J = 8.3, 1.1 Hz, 1H), (m, 2H), (m, 1H), 7.16 (td, J = 7.8, 1.6 Hz, 1H), 6.99 (td, J = 7.4, 1.2 Hz, 1H), (m, 1H), 2.79 (q, J = 7.5 Hz, 2H), 1.32 (t, J = 7.5 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , 24.89, 14.30; IR (KBr) v 3248, 3060, 2963, 1585, 1455, 1266, 1093 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 19 H 18 N 2, , found (Tert-butyl)-N-(2-(pyridin-2-yl)phenyl)aniline (3r): Yield 92% (41.7 mg), purified by chromatography on silica gel (5:1 Hexanes/DCM), orange oil, TLC R f = 0.4 (5:1 Hexanes/DCM); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.56 (d, J = 4.8 Hz, 1H), (m, 2H), 7.68 (dd, J = 7.9, 1.5 Hz, 1H), 7.47 (dd, J = 7.9, 1.5 Hz, 1H), 7.34 (dd, J = 7.9, 1.4 Hz, 1H), (m, 3H), 21

22 (m, 2H), (m, 1H), 1.53 (s, 9H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , 34.85, 30.29; IR (KBr) v 3269, 3060, 1607, 1580, 1393, 1197, 935 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 21 H 22 N 2, , found N-(2-(pyridin-2-yl)phenyl)-[1,1'-biphenyl]-2-amine (3s): Yield 96% (46.4 mg), purified by chromatography on silica gel (15:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.50 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 7.95 (d, J = 4.8 Hz, 1H), 7.66 (m, 3H), (m, 6H), 7.42 (dd, J = 9.4, 4.4 Hz, 1H), (m, 3H), (m, 1H), 6.97 (t, J = 7.4 Hz, 1H), 6.92 (t, J = 7.5 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , ; IR (KBr) v 3238, 3028, 1748, 1586, 1558, 1477, 1422, 1112, 1076 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 23 H 18 N 2, , found Methoxy-N-(2-(pyridin-2-yl)phenyl)aniline (3t): Yield 90% (37.3 mg), purified by chromatography on silica gel (5:1 Hexanes/EtOAc), orange solid, TLC R f = 0.20 (5:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.70 (d, J = 4.1 Hz, 1H), 7.79 (td, J = 7.8, 1.8 Hz, 1H), 7.70 (d, J =

23 Hz, 1H), 7.62 (dd, J = 7.8, 1.4 Hz, 1H), 7.57 (d, J = 7.9 Hz, 1H), 7.43 (dd, J = 6.1, 3.2 Hz, 1H), (m, 1H), 7.23 (ddd, J = 7.3, 4.9, 0.9 Hz, 1H), (td, J = 7.5, 0.9 Hz, 1H), (m, 3H), 3.95 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , 55.86; IR (KBr) v 3265, 3005, 1587, 1560, 1461, 1263, 1046 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 16 N 2 O, , found N-(2-(pyridin-2-yl)phenyl)naphthalen-1-amine (3u): Yield 92% (40.9 mg) (48h), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), brown solid, TLC R f = 0.30 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.68 (d, J = 4.7 Hz, 1H), 8.31 (d, J = 8.6 Hz, 1H), (m, 1H), 7.81 (d, J = 3.5 Hz, 2H), 7.72 (d, J = 7.7 Hz, 1H), (m, 4H), (m, 2H), (m, 2H), 6.94 (t, J = 7.4 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , ; IR (KBr) v 3240, 1719, 1579, 1504, 1220, 1123, 1057 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 21 H 16 N 2, , found N-(2-bromophenyl)-4-methyl-2-(pyridin-2-yl)aniline (4a): 23

24 Yield 99% (50.4 mg), purified by chromatography on silica gel (20:1 Hexanes/EtOAc), brown solid, TLC R f = 0.67 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.71 (dd, J = 4.9, 0.8 Hz, 1H), 7.76 (td, J = 7.8, 1.8 Hz, 1H), 7.68 (d, J = 8.1 Hz, 1H), 7.53 (dd, J = 7.9, 1.4 Hz, 1H), 7.46 (d, J = 8.4 Hz, 2H), 7.37 (dd, J = 8.2, 1.4 Hz, 1H), 7.21 (ddd, J = 7.4, 4.9, 1.0 Hz, 1H), 7.14 (m, 2H), 6.69 (td, J = 7.9, 1.4 Hz, 1H), 2.40 (s, 3H).; 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , 20.79; IR (KBr) v 3226, 3014, 1587, 1564, 1420, 1222, 1021 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 15 BrN 2, , found Ethyl 4-((2-bromophenyl)amino)-3-(pyridin-2-yl)benzoate (4b): Yield 95% (56.6 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.40 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.68 (d, J = 4.8 Hz, 1H), 8.42 (s, 1H), 7.93 (d, J = 8.7 Hz, 1H), 7.85 (m, 2H), 7.60 (d, J = 7.9 Hz, 1H), 7.47 (d, J = 8.1 Hz, 1H), 7.42 (d, J = 8.7 Hz, 1H), (m, 2H), 6.86 (t, J = 7.6 Hz, 1H), 4.38 (q, J = 7.1 Hz, 2H), 1.41 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , 60.60, 14.45; IR (KBr) v 3199, 3064, 1707, 1610, 1587, 1455, 1365, 1240, 1111 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 20 H 17 BrN 2 O 2, , found

25 4-((2-Bromophenyl)amino)-3-(pyridin-2-yl)benzaldehyde (4c): Yield 96% (50.9 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.21 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 9.87 (s, 1H), 8.68 (d, J = 4.5 Hz, 1H), 8.25 (d, J = 1.5 Hz, 1H), 7.87 (m, 2H), 7.74 (d, J = 8.6 Hz, 1H), 7.64 (d, J = 7.9 Hz, 1H), 7.49 (d, J = 7.7 Hz, 1H), 7.42 (d, J = 8.6 Hz, 1H), 7.28 (dd, J = 12.2, 5.5 Hz, 2H), 6.94 (t, J = 7.3 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , ; IR (KBr) v 3222, 3061, 1682, 1574, 1455, 1134, 1045 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 13 BrN 2 O, , found ((2-Bromophenyl)amino)-3-(pyridin-2-yl)phenyl (4d): 4-methylbenzenesulfonate Yield 90% (66.9 mg), purified by chromatography on silica gel (5:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.68 (2:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.68 (d, J = 4.3 Hz, 1H), 7.77 (m, 3H), 7.54 (dd, J = 7.9, 1.1 Hz, 1H), 7.48 (d, J = 8.1 Hz, 1H), (m, 5H), 7.25 (dd, J = 7.1, 4.8 Hz, 1H), 7.15 (t, J = 7.7 Hz, 1H), 6.81 (dd, J = 9.0, 2.7 Hz, 1H), 6.75 (t, J = 7.6 Hz, 1H), 2.45 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , 21.67; IR (KBr) v 3481, 3005, 1586, 1475, 1455, 1318, 25

26 1092 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 24 H 19 BrN 2 O 3 S, , found ((2-Bromophenyl)amino)-3-(pyridin-2-yl)phenyl (4e): trifluoromethanesulfonate Yield 95% (67.4 mg) (48h), purified by chromatography on silica gel (3:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.29 (3:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.72 (d, J = 4.2 Hz, 1H), 7.85 (td, J = 7.9, 1.5 Hz, 1H), 7.69 (d, J = 8.1 Hz, 1H), 7.58 (dd, J = 8.0, 1.4 Hz, 1H), 7.55 (d, J = 2.9 Hz, 1H), 7.48 (d, J = 9.1 Hz, 1H), 7.40 (dd, J = 8.2, 1.3 Hz, 1H), 7.30 (dd, J = 7.0, 5.2 Hz, 1H), (m, 2H), 6.82 (td, J = 8.0, 1.4 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , ; IR (KBr) v 3454, 1871, 1785, 1585, 1561, 1443, 1321, 1096 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 12 BrF 3 N 2 O 3 S, , found N-(2-bromophenyl)-4-((tert-butyldimethylsilyl)oxy)-2-(pyridin-2-yl)aniline (4f): Yield 96% (65.6 mg)(48h), purified by chromatography on silica gel (20:1 Hexanes/EtOAc) yellow solid, TLC R f = 0.70 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 9.91 (s, 1H), 8.70 (d, J = 4.8 Hz, 1H), 7.77 (t, J = 7.7 Hz, 1H), 7.60 (d, 26

27 J = 8.0 Hz, 1H), 7.48 (d, J = 7.9 Hz, 1H), 7.41 (d, J = 8.8 Hz, 1H), (m, 2H), 7.10 (m, 2H), 6.85 (dd, J = 8.8, 2.7 Hz, 1H), 6.63 (t, J = 7.6 Hz, 1H), 1.02 (s, 9H), 0.23 (s, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , 25.74, 18.21, -4.36; IR (KBr) v 3248, 2885, 1587, 1563, 1515, 1440, 1361, 1286, 1021 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 23 H 27 BrN 2 OSi, , found N-(2-bromophenyl)-3-methyl-2-(pyridin-2-yl)aniline (4g): Yield 98% (49.9 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), brown oil, TLC R f = 0.46 (10:1 Hexanes/EtOAc). 1 H NMR (400 MHz, CDCl 3 ) δ (d,j = 4.9 Hz 1H), 7.76 (td, J = 7.7, 1.8 Hz, 1H), 7.42 (dd, J = 7.9, 1.4 Hz, 1H), 7.34 (m, 2H), (m, 3H), 7.17 (s, 1H), (m, 1H), 6.98 (d, J = 7.4 Hz, 1H), 6.65 (td, J = 7.9, 1.5 Hz, 1H), 2.22 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , 20.67; IR (KBr) v 3350, 3061, 1654, 1579, 1430, 1379, 1121, 1093 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 15 BrN 2, , found N-(2-bromophenyl)-3-(pyridin-2-yl)naphthalen-2-amine (4h) Yield 98% (55.2 mg), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), orange solid, TLC R f = 0.40 (10:1 Hexanes/EtOAc); 1 H NMR (400 27

28 MHz, CDCl 3 ) δ (s, 1H), 8.76 (d, J = 4.8 Hz, 1H), 8.10 (s, 1H), 7.83 (m, 4H), 7.67 (d, J = 8.2 Hz, 1H), (m, 2H), 7.45 (t, J = 7.3 Hz, 1H), 7.34 (t, J = 7.4 Hz, 1H), 7.30 (dd, J = 8.7, 4.7 Hz, 1H), 7.20 (t, J = 7.7 Hz, 1H), 6.76 (t, J = 7.6 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , ; IR (KBr) v 3225, 3005, 1632, 1584, 1487, 1433, 1022 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 21 H 15 BrN 2, , found Bromo-N-(2-(5-methylpyridin-2-yl)phenyl)aniline (4i): Yield 94% (47.8 mg), purified by chromatography on silica gel (15:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.56 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.54 (s, 1H), (m, 3H), (m, 2H), 7.42 (d, J = 8.1 Hz, 1H), 7.29 (t, J = 8.0 Hz, 1H), 7.14 (t, J = 7.4 Hz, 1H), 7.01 (t, J = 7.5 Hz, 1H), 6.71 (t, J = 7.6 Hz, 1H), 2.38 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , 18.16; IR (KBr) v 3223, 3020, 1582, 1560, 1426, 1283,1043 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 15 BrN 2, , found N-(2-bromophenyl)-3-methoxy-2-(5-methylpyridin-2-yl)aniline (4j): 28

29 Yield 96% (53.2 mg), Purified by chromatography on silica gel (10:1 Hexanes/EtOAc), yellow oil, TLC R f = 0.30 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 8.98 (s, 1H), 8.58 (s, 1H), 7.54 (d, J = 1.3 Hz, 2H), 7.46 (dd, J = 7.9, 1.4 Hz, 1H), 7.33 (dd, J = 8.2, 1.3 Hz, 1H), (m, 1H), (m, 2H), (m, 2H), 3.80 (s, 3H), 2.37 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , 55.79, 18.29; IR (KBr) v 3284, 3002, 1581, 1518, 1447, 1373, 1183 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 19 H 17 BrN 2 O, , found N-(2-bromophenyl)-2-(5-fluoropyridin-2-yl)-4-methylaniline (4k): Yield 98% (52.5 mg), purified by chromatography on silica gel (20:1 Hexanes/EtOAc), brown solid, TLC R f = 0.68 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 9.77 (s, 1H), 8.56 (d, J = 2.9 Hz, 1H), 7.67 (dd, J = 8.8, 4.3 Hz, 1H), 7.50 (m, 2H), 7.41 (m, 2H), 7.31 (dd, J = 8.2, 1.1 Hz, 1H), (m, 2H), 6.68 (td, J = 7.9, 1.4 Hz, 1H), 2.38 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ (d, J = 254.4), (d, J = 4.1 Hz), , , (d, J = 23.9Hz), , , , , , , (d, J = 18.5 Hz), (d, J = 4.2 Hz),120.45, , , , 20.80; IR (KBr) v 3259, 1588, 1404, 1382, 1142, 1044, 907 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 18 H 14 BrFN 2, , found N-(4-nitrophenyl)-2-(pyrimidin-2-yl)aniline (4l): 29

30 Yield 93% (40.8 mg), purified by chromatography on silica gel (15:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.31 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ (s, 1H), 8.85 (d, J = 4.9 Hz, 2H), 8.53 (dd, J = 8.0, 1.4 Hz, 1H), 8.15 (d, J = 9.1 Hz, 2H), 7.59 (d, J = 8.2 Hz, 1H), (m, 1H), (m, 3H), 7.14 (t, J = 7.6 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , ; IR (KBr) v 3288, 3005, 1629, 1577, 1483, 1365, 1185, 1111 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 16 H 12 N 4 O 2, , found (E)-1-(2-((2-bromophenyl)amino)phenyl)ethan-1-one O-methyl oxime (4m): Yield 90% (43.1 mg) (48h), purified by chromatography on silica gel (30:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.45 ( 20:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 9.37 (s, 1H), 7.57 (d, J = 8.0 Hz, 1H), (m, 3H), (m, 2H), 6.94 (t, J = 7.5 Hz, 1H), 6.79 (t, J = 7.6 Hz, 1H), 4.09 (s, 3H), 2.30 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , 62.45, 13.92; IR (KBr) v 3274, 2816, 1602, 1583, 1478, 1186, 1075 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 15 H 15 BrN 2 O, , found

31 (2R,3R,4R,5R)-2-(acetoxymethyl)-5-(6-(2-((2 bromophenyl)amino)phenyl)-9h-purin-9-yl)tetrahydrofuran-3,4-diyl (4n): diacetate Yield 68% (63.7 mg) (48 h), purified by chromatography on silica gel (3:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.58 (1:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 9.05 (s, 1H), 8.84 (dd, J = 8.0, 1.4 Hz, 1H), 8.30 (s, 1H), 7.57 (dd, J = 8.0, 1.4 Hz, 1H), 7.51 (d, J = 8.3 Hz, 1H), 7.44 (dd, J = 8.2, 1.3 Hz, 1H), (m, 1H), 7.17 (t, J = 7.7 Hz, 1H), 7.09 (t, J = 7.6 Hz, 1H), 6.78 (td, J = 8.0, 1.4 Hz, 1H), 6.31 (d, J = 5.4 Hz, 1H), 6.01 (t, J = 5.5 Hz, 1H), 5.70 (t, J = 5.2 Hz, 1H), (m, 3H), 2.16 (s, 3H), 2.14 (s, 3H), 2.08 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , 86.33, 80.45, 73.07, 70.67, 63.06, 20.75, 20.52, 20.36; IR (KBr) v 1750, 1584, 1520, 1434, 1371, 1312, 1096, 1023 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 28 H 26 BrN 5 O 7, , found General Procedure for the diamination To a Schlenk tube equipped with a teflon plug valve and stirbar was added the monosubstituted product 3 (0.1 mmol), Ar 2 N 3 (0.12 mmol), [RhCp*Cl 2 ] 2 (2.5 mg, 4 31

32 mol %), NaBARF (3.5 mg, 4 mol %) and H 2 O (1 ml) under atmospheric conditions. The reaction mixture was vigorously stirred on a pre-heated oil bath at 110 o C for 48 h. The reaction was cooled to room temperature, diluted with CH 2 Cl 2 (10 ml) and then washed by water (5 ml x 3).The aqueous layer was extracted by CH 2 Cl 2 (5 ml x 3). The solvents were removed under reduced pressure and the crude reaction mixture was purified by silica gel column chromatography (n-hexane/etoac) as an eluent to give the disubstituted product 5. N1,N3-bis(2-bromophenyl)-2-(pyridin-2-yl)benzene-1,3-diamine (5a): Yield 90% (44.6 mg)(48h), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), brown solid, TLC R f = 0.29 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 8.77 (d, J = 4.8 Hz, 1H), 7.67 (t, J = 7.7 Hz, 1H), 7.52 (d, J = 7.9 Hz, 1H), 7.45 (d, J = 7.9 Hz, 2H), (m, 10H), 6.68 (t, J = 7.6 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , ; IR (KBr) v 3440, 3005, 1641, 1454, 1275, 1260, 1032, 1016 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 23 H 17 Br 2 N 3, , found N1-(2-bromophenyl)-N3-(2-methoxyphenyl)-2-(pyridin-2-yl)benzene-1,3-diamine (5b): Yield 96% (42.8 mg)(48h), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), brown solid, TLC R f = 0.38 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 8.77 (d, J = 4.7 Hz, 1H), 7.67 (t, J = 7.7 Hz, 1H), 7.53 (d, J = 7.9 Hz, 1H), 7.43 (d, J = 7.9 Hz, 1H), (m, 6H), 7.11 (t, J = 7.7 Hz, 1H), 7.05 (d, J 32

33 = 7.8 Hz, 1H), (m, 4H), 6.66 (t, J = 7.6 Hz, 1H), 3.79 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , , , , 55.68; IR (KBr) v 3500, 3005, 1643, 1577, 1505, 1474, 1428, 1275, 1016 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 24 H 20 BrN 3 O, , found Ethyl 4-((3-((2-bromophenyl)amino)-2-(pyridin-2-yl)phenyl)amino)benzoate (5c): Yield 96% (46.9 mg)(48h), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), brown solid, TLC R f = 0.40 (4:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 8.75 (d, J = 4.7 Hz, 1H), 7.89 (d, J = 8.5 Hz, 2H), 7.67 (t, J = 7.7 Hz, 1H), 7.47 (dd, J = 12.4, 7.9 Hz, 2H), (m, 7H), 7.04 (s, 1H), 6.96 (d, J = 8.5 Hz, 2H), 6.69 (t, J = 7.6 Hz, 1H), 4.33 (q, J = 7.1 Hz, 2H), 1.37 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , , , 60.41, 14.41; IR (KBr) v 3346, 3052, 1703, 1605, 1574, 1392, 1212, 1049 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 26 H 22 BrN 3 O 2, , found N1-(2-bromophenyl)-N3-(4-nitrophenyl)-2-(pyridin-2-yl)benzene-1,3-diamine (5d): Yield 72% (33.2 mg) (48h), purified by chromatography on silica gel (4:1 Hexanes/EtOAc), yellow solid, TLC R f = 0.20 (4:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 8.72 (d, J = 4.7 Hz, 1H), 8.06 (d, J = 9.1 Hz, 2H), 7.70 (t, J = 7.7 Hz, 33

34 1H), 7.54 (s, 1H), 7.47 (t, J = 7.5 Hz, 2H), 7.33 (t, J = 8.1 Hz, 1H), (m, 3H), 7.14 (m, 2H), 7.05 (s, 1H), 6.90 (d, J = 9.1 Hz, 2H), 6.71 (t, J = 7.6 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , ; IR (KBr) v 3373, 3356, 1579, 1501, 1477, 1430, 1306, 1181 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 23 H 17 BrN 4 O 2, , found Ethyl 3-bromo-4-((3-((2-bromophenyl)amino)-2-(pyridin-2-yl)phenyl)amino) benzoate (5e): Yield 92% (44.9 mg)(48h), purified by chromatography on silica gel (10:1 Hexanes/EtOAc), brown solid, TLC R f = 0.50 (4:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 8.77 (d, J = 4.5 Hz, 1H), 8.12 (d, J = 1.8 Hz, 1H), 7.78 (dd, J = 8.7, 1.7 Hz, 1H), 7.67 (t, J = 7.2 Hz, 1H), 7.60 (s, 1H), 7.47 (d, J = 4.6 Hz, 1H), 7.46 (d, J = 3.9 Hz, 1H), 7.33 (t, J = 8.1 Hz, 1H), (m, 7H), 6.71 (t, J = 7.1 Hz, 1H), 4.32 (q, J = 7.1 Hz, 2H), 1.36 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , , , , , 60.71, 14.36; IR (KBr) v 3387, 3061, 1708, 1580, 1471, 1408, 1172, 1037 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 26 H 21 Br 2 N 3 O 2, , found N1-(2-bromophenyl)-N3-(4-chloro-2-iodophenyl)-2-(pyridin-2-yl)benzene-1,3-dia mine (5f): 34

35 Yield 96% (55.4 mg)(48h), purified by chromatography on silica gel (20:1 Hexanes/EtOAc), brown solid, TLC R f = 0.48 (10:1 Hexanes/EtOAc); 1 H NMR (400 MHz, CDCl 3 ) δ 8.78 (d, J = 4.7 Hz, 1H), (m, 2H), 7.51 (d, J = 7.9 Hz, 1H), 7.46 (d, J = 7.9 Hz, 1H), (m, 3H), (m, 6H), 7.01 (d, J = 8.0 Hz, 1H), 6.70 (t, J = 7.6 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ , , , , , , , , , , , , , , , , , , , , , 88.17; IR (KBr) v 3383, 3061, 1579, 1494, 1575, 1400, 1377, 1022 cm -1 ; HRMS (ESI) ([M+H] + ) calcd. for C 23 H 16 BrClIN 3, , found One-pot Cascade Diamination Reaction (Scheme 4) To a Schlenk tube equipped with a teflon plug valve and stirbar was added 2-phenylpyridine (15.5 mg, 0.1 mmol), 1-azido-2-bromobenzene (19.8 mg, 0.1 mmol), [RhCp*Cl 2 ] 2 (2.5 mg, 4 mol %), NaBARF (3.5 mg, 4 mol%) and H 2 O (1 ml) under atmospheric conditions. The reaction mixture was vigorously stirred on a pre-heated oil bath at 110 o C for 24 h and then added [RhCp*Cl 2 ] 2 (2.5 mg, 4 mol %), NaBARF (3.5 mg, 4 mol%) and 1-azido-2-methoxybenzene (23.8 mg, 0.12 mmol) to the reaction mixture and continued stirring for additional 48 h. Then the reaction was cooled to room temperature, diluted with CH 2 Cl 2 (10 ml) and then washed by water (5 ml x 3).The aqueous layer was extracted by CH 2 Cl 2 (5 ml x 3). The solvents were removed under reduced pressure and the crude reaction mixture was purified by silica gel chromatography using (n-hexane/etoac) as an eluent to get the disubstituted product 5a (32.2 mg). 35

36 Schemes S1-S4 To a Schlenk tube equipped with a teflon plug valve and stirbar was added 2-phenylpyridine (15.5 mg, 0.1 mmol), arylazide (19.1 mg, 0.1 mmol), [RhCp*Cl 2 ] 2 (2.5 mg, 4 mol %), NaBARF (3.5 mg, 4 mol%), 3a or 3l (40 mol %) and water (1 ml) under atmospheric conditions. The reaction mixture was vigorously stirred on a pre-heated oil bath at 110 o C for 24 h. The reaction was cooled to room temperature, extracted with CH 2 Cl 2 (10 ml). The solvents were removed under reduced pressure and the crude reaction mixture was purified by silica gel column chromatography (n-hexane/etoac) as an eluent to get the desired product 3b (62%, 19.7 mg). To a Schlenk tube equipped with a teflon plug valve and stirbar was added 2-phenylpyridine (15.5 mg, 0.1 mmol), 1-azido-4-nitrobenzene (16.4 mg, 0.1 mmol), 1-azido-2-methoxybenzene (14.9 mg, 0.1 mmol), [RhCp*Cl 2 ] 2 (2.5 mg, 4 mol %), NaBARF (3.5 mg, 4 mol%), and water (1 ml) under atmospheric conditions. The reaction mixture was vigorously stirred on a pre-heated oil bath at 110 o C for 24 h. The reaction was cooled to room temperature, extracted with CH 2 Cl 2 (10 ml). The solvents were removed under reduced pressure and the crude reaction mixture was 36

37 purified by silica gel column chromatography (n-hexane/etoac) as an eluent to get the desired products 3a and 3t. To a Schlenk tube equipped with a teflon plug valve and stirbar was added 2-phenylpyridine (15.5 mg, 0.1 mmol), 1-azido-4-nitrobenzene (16.4 mg, 0.1 mmol), 1-azido-4-methoxybenzene (14.9 mg, 0.1 mmol), [RhCp*Cl 2 ] 2 (2.5 mg, 4 mol %), NaBARF (3.5 mg, 4 mol%), and water (1 ml) under atmospheric conditions. The reaction mixture was vigorously stirred on a pre-heated oil bath at 110 o C for 24 h. The reaction was cooled to room temperature, extracted with CH 2 Cl 2 (10 ml). The solvents were removed under reduced pressure and the crude reaction mixture was purified by silica gel column chromatography (n-hexane/etoac) as an eluent to get the desired products 3a and 3l. Preliminary Mechanistic Study (Scheme 5 and Scheme S5) On Water: A mixture of [RhCp*Cl 2 ] 2 (123.6 mg, 0.2 mmol), 2-phenylpyridine (124.2 mg, 0.8 mmol ) and H 2 O (5 ml) were stirred at 110 o C for 6 h. The mixture was extracted with dichloromethane (5 ml x 3) and organic layer then filtered through a plug of celite washing with dichloromethane (5 ml x 3). The solvents were removed under reduced pressure and then washed with hexane (10 ml x 5). A cyclometalated compound (6) was obtained as a red-orange solid (169.4 mg, 99%). In DCE: [4] A mixture of [RhCp*Cl 2 ] 2 (123.6 mg, 0.2 mmol ), 2-phenylpyridine (124.2 mg, 0.8 mmol ) in 1,2-dichloroethane (5 ml)were stirred at 110 o C for 6 h. The mixture was filtered through a plug of celite washing with dichloromethane (5 ml x 3). The solvents were removed under reduced 37