indium(III)bromide → Benzyl 4-(6-(5-bromo-4-(2-ethoxy-2-oxoethyl)thiophene-2-carbonyl)-1H-indol-2-yl)benzoate

HRID 1952492Notes

Reaction equation

HRID 1952492 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([C:8]([C:10]2[S:11][C:12]([Br:21])=[C:13]([CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH:14]=2)=[O:9])[CH:5]=[CH:4][C:3]=1[C:22]#[C:23][C:24]1[CH:39]=[CH:38][C:27]([C:28]([O:30][CH2:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)=[O:29])=[CH:26][CH:25]=1.[Br-].[Br-].[Br-].[In+3]>C1(C)C=CC=CC=1>[Br:21][C:12]1[S:11][C:10]([C:8]([C:6]2[CH:7]=[C:2]3[C:3]([CH:22]=[C:23]([C:24]4[CH:25]=[CH:26][C:27]([C:28]([O:30][CH2:31][C:32]5[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=5)=[O:29])=[CH:38][CH:39]=4)[NH:1]3)=[CH:4][CH:5]=2)=[O:9])=[CH:14][C:13]=1[CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17]

Participants

4

Reactant 2

HCID 167051indium(III)bromideHCID 67496516Benzyl 4-((2-amino-4-(5-bromo-4-(2-ethoxy-2-oxoethyl)thiophene-2-carbonyl)phenyl)ethynyl)benzoate

Product 1

HCID 67496556Benzyl 4-(6-(5-bromo-4-(2-ethoxy-2-oxoethyl)thiophene-2-carbonyl)-1H-indol-2-yl)benzoateYield 76%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a 25 mL flask containing freshly distilled toluene (10 mL) was added benzyl 4-((2-amino-4-(5-bromo-4-(2-ethoxy-2-oxoethyl)thiophene-2-carbonyl)phenyl)ethynyl)benzoate (100 mg, 0.17 mmol) and indium tribromide (24 mg, 0.06 mmol) under N2. The resulting mixture was refluxed for one hour. The solvent was removed in vacuo. MPLC purification (Hex:EtOAc/4:1) of the crude product gave 4 as a yellow solid (76 mg, 76%). 1H NMR (400 MHz, CDCl3) δ 9.50 (brs, 1H), 8.16 (d, J=8.0 Hz, 2H), 8.02 (s, 1H), 7.82 (d, J=8.4 Hz, 2H), 7.65 (q, J=8.4 Hz, 2H), 7.55 (s, 1H), 7.48-7.34 (m, 5H), 6.98 (s, 1H), 5.39 (s, 2H), 4.19 (q, J=7.2 Hz, 2H), 3.64 (s, 2H), and 1.28 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 187.53, 170.09, 166.24, 143.98, 140.75, 136.91, 136.16, 136.07, 135.92, 135.09, 132.96, 131.53, 130.74, 129.74, 128.90, 128.59, 128.53, 125.56, 122.10, 121.94, 120.81, 113.74, 101.86, 67.14, 61.66, 35.37, and 14.43.

Workup

  1. temperatureThe resulting mixture was refluxed for one hour
  2. customThe solvent was removed in vacuo
  3. customMPLC purification (Hex:EtOAc/4:1) of the crude product

Sources & evidence

ORD record
ord-f187d523b9154073b4b9b892fb7a3481
Source dataset
uspto-grants-2013_03
Patent number
US08404728B2

Reaction notes

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