D to reflux at 160 for 12 h. The o-dichlorobenzene was removed by basic distillation, plus the resulting dark colored strong was subjected to flash chromatography employing a prepacked 50 g silica column [solvent A: EtOAc; solvent B: hexanes; gradient: 7 A / 93 B (four CV), 7 A / 93 B 60 A / 40 B (ten CV), 60 A / 40 B (2 CV); flow rate: 40 mL/min; monitored at 254 and 280 nm] resulting in di-TBS-indole 21 as a pale yellow powder (0.04 g, 0.59 mmol, 20 , Rf = 0.33 (70:30 hexanes:EtOAc)). 1H NMR (CDCl3, 500 MHz): 8.31 (br s, 1H, NH), 7.90 (d, J = 8.five Hz, 1H, ArH), 6.99 (s, 2H, ArH) 6.94 (dd, J = eight.five Hz, two.0 Hz, 1H, ArH), six.89 (d, J = 2.0 Hz, 1H, ArH), 6.82 (dd, J = eight.five Hz, 2.0 Hz, 1H, ArH), 6.76 (d, J = 2.five Hz, 1H, ArH), 6.70 (d, J = eight.0 Hz, 1H, ArH), three.79 (s, 3H, OCH3), three.75 (s, 3H, OCH3), three.69 (s, 6H, OCH3), 1.01 (s, 9H, C(CH3)three), 0.94 (s, 9H, C(CH3)three), 0.22 (s, 6H, Si(CH3)2), 0.Ginsenoside Rb2 04 (s, 6H, Si(CH3)two). 13C NMR (CDCl3, 125 MHz): 191.eight, 153.0, 152.6, 151.7, 145.two, 142.three, 141.3, 136.five, 134.6, 125.two, 123.9, 122.three, 121.9, 116.7, 112.9, 111.eight, 107.four, 105.1, 101.6, 60.9, 56.1, 55.five, 25.9, 25.eight, 18.46, 18.45, -4.two, -4.eight. HPLC: 23.31 min., purity at 254 nm 90.6 . HRMS (ESI+): m/z calculated for C37H52NO7Si2 [M+H]+ 678.3277, found 678.3279. 4.1.18. 2-(3-tert-Butyldimethylsiloxy-4-methoxyphenyl)-3-(three,four,5trimethoxybenzoyl)-4,5,6-trimethoxyindole (22)–To a option of compound 7 (0.05 g, 0.11 mmol) in o-dichlorobenzene (10 mL) was added 3,4,5-trimethoxybenzoyl chloride (0.04 g, 0.17 mmol). The reaction mixture was heated to reflux at 160 for 12 h. The odichlorobenzene was removed by straightforward distillation, along with the resulting dark green colored strong was subjected to flash chromatography working with a prepacked 25 g silica column [solvent A: EtOAc; solvent B: hexanes; gradient: 12 A / 88 B (4 CV), 12 A / 88 B 100 A / 0 B (10 CV), one hundred A / 0 B (two CV); flow price: 25 mL/min; monitored at 254 and 280 nm] resulting in TBS-indole 22 as a pale yellow powder (0.03 g, 0.05 mmol, 46 , Rf = 0.50 (50:50 hexanes:EtOAc)). 1H NMR (CDCl3, 500 MHz): eight.25 (br s, 1H, NH), 7.19 (s, 2H,Bioorg Med Chem. Author manuscript; available in PMC 2014 November 01.MacDonough et al.PageArH), six.99 (dd, J = 8.five Hz, two.five Hz, 1H, ArH), 6.88 (d, J = two.Ixekizumab 5 Hz, 1H, ArH), six.75 (d, J = eight.0 Hz, 1H, ArH), six.69 (s, 1H, ArH), 3.90 (s, 3H, OCH3), 3.85 (s, 3H, OCH3), three.82 (s, 3H, OCH3), 3.76 (s, 3H, OCH3), three.74 (s, 6H, OCH3), three.72 (s, 3H, OCH3), 0.93 (s, 9H, C(CH3)3), 0.04 (s, 6H, Si(CH3)2). 13C NMR (CDCl3, 125 MHz): 193.4, 152.9, 152.1, 151.4, 146.four, 145.3, 142.2, 137.eight, 136.six, 134.2, 132.four, 124.7, 121.1, 120.PMID:24818938 5, 116.7, 114.four, 112.3, 107.6, 89.8, 61.four, 61.0, 60.eight, 56.four, 56.3, 55.six, 25.eight, 18.five, -4.7. HPLC: 18.60 min., purity at 254 nm 90.7 . HRMS (ESI+): m/z calculated for C34H44NO9Si [M+H]+ 638.2780, discovered 638.2780. 4.1.19. 2-(4-Methoxyphenyl)-3-(three,4,5-trimethoxybenzoyl)-6-methoxy-7-tertbutyldimethylsilyloxyindole (23)–To a option of compound 10 (0.05 g, 0.13 mmol) in o-dichlorobenzene (10 mL) was added 3,four,5-trimethoxybenzoyl chloride (0.05 g, 0.20 mmol). The reaction mixture was heated to reflux at 160 for 12 h. The o-dichlorobenzene was removed by basic distillation, and also the resulting dark green colored strong was subjected to flash chromatography making use of a prepacked 25 g silica column [solvent A: EtOAc; solvent B: hexanes; gradient: ten A / 90 B (four CV), 10 A / 90 B 80 A / 20 B (ten CV), 80 A / 20 B (two CV); flow rate: 25 mL/min; monitored at 254 and 280 nm] resulting in TBS-indole 23 as a yellow powder (0.