6-Nitro-1-[2-(trimethyl-silanyl)-ethoxymethyl]-3-(trimethyl-stannanyl)-1-H-indazole → 6-nitro-1-[2-(trimethyl-silanyl)ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazole

HRID 724397Notes

Reaction equation

HRID 724397 reaction equation
[N+:1]([C:4]1[CH:12]=[C:11]2[C:7]([C:8]([Sn](C)(C)C)=[N:9][N:10]2[CH2:13][O:14][CH2:15][CH2:16][Si:17]([CH3:20])([CH3:19])[CH3:18])=[CH:6][CH:5]=1)([O-:3])=[O:2].I[N:26]1[C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][C:29]=2[N:28]([CH2:35][O:36][CH2:37][CH2:38][Si:39]([CH3:42])([CH3:41])[CH3:40])[CH2:27]1>[Cu]I.C1COCC1>[N+:1]([C:4]1[CH:12]=[C:11]2[C:7]([C:8]([C:27]3[N:28]([CH2:35][O:36][CH2:37][CH2:38][Si:39]([CH3:41])([CH3:42])[CH3:40])[C:29]4[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=4[N:26]=3)=[N:9][N:10]2[CH2:13][O:14][CH2:15][CH2:16][Si:17]([CH3:20])([CH3:19])[CH3:18])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 2

HCID 218774146-Nitro-1-[2-(trimethyl-silanyl)-ethoxymethyl]-3-(trimethyl-stannanyl)-1-H-indazoleHCID 218775973-iodo-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzimidazole

Product 1

HCID 229806876-nitro-1-[2-(trimethyl-silanyl)ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazoleYield 82.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent

Procedure

6-Nitro-1-[2-(trimethyl-silanyl)-ethoxymethyl]-3-(trimethyl-stannanyl)-1-H-indazole (7.50 g, 16.4 mmol), 3-iodo-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzimidazole (6.50 g, 17.4 mmol), and copper(I) iodide (313 mg, 1.64 mmol) were combined with dry THF (150 mL) in a flask purged with argon. Tetrakis(triphenylphosphine)palladium(0) was added, and the reaction stirred at reflux under argon for 23 h. The reaction was cooled and adsorbed directly onto silica gel (˜16 g). Purification by silica gel chromatography (4% to 15% ethyl acetate/hexanes) gave 7.28 g (82%) of 6-nitro-1-[2-(trimethyl-silanyl)-ethoxymethyl]-3-{1-[2-(trimethyl-silanyl)-ethoxymethyl]-1-H-benzoimidazol-2-yl}-1-H-indazole as a light yellow solid. 1H NMR (300 MHz, CDCl3) δ 8.91 (d, 1 H, J=9.0 Hz), 8.59 (d, 1 H, J=1.8 Hz), 8.22 (dd, 1 H, J=8.7, 1.8 Hz), 7.92–7.89 (m, 1 H), 7.66–7.62 (m, 1 H), 7.40–7.36 (m, 2 H), 6.24 (s, 2 H), 5.90 (s, 2 H), 3.68–3.59 (m, 4 H), 0.94 (t, 2 H, J=8.1 Hz), 0.86 (t, 2 H, J=8.1 Hz), −0.04 (s, 9 H), −0.15 (s, 9 H). Anal. (C26H37N5O4Si2) C, H, N. Calculated: C, 57.85; H, 6.91; N, 12.97. Found: C, 57.60; H, 6.81; N, 12.82.

Workup

  1. custompurged with argon
  2. additionTetrakis(triphenylphosphine)palladium(0) was added
  3. temperatureat reflux under argon for 23 h
  4. temperatureThe reaction was cooled
  5. customPurification by silica gel chromatography (4% to 15% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-919c6821b04944e1af013e265424bddd
Source dataset
uspto-grants-2006_11
Patent number
US07141587B2

Reaction notes

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