Sodium Chloride → 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine

HRID 1469084Notes

Reaction equation

HRID 1469084 reaction equation
[CH3:1][C:2]1([CH3:18])[C:6]([CH3:8])([CH3:7])[O:5][B:4]([C:9]2[CH:10]=[C:11]3[CH:17]=[CH:16][NH:15][C:12]3=[N:13][CH:14]=2)[O:3]1.[H-].[Na+].Cl[Si:22]([CH:29]([CH3:31])[CH3:30])([CH:26]([CH3:28])[CH3:27])[CH:23]([CH3:25])[CH3:24].[Cl-].[Na+]>O1CCCC1>[CH3:8][C:6]1([CH3:7])[C:2]([CH3:18])([CH3:1])[O:3][B:4]([C:9]2[CH:10]=[C:11]3[CH:17]=[CH:16][N:15]([Si:22]([CH:29]([CH3:31])[CH3:30])([CH:26]([CH3:28])[CH3:27])[CH:23]([CH3:25])[CH3:24])[C:12]3=[N:13][CH:14]=2)[O:5]1

Participants

6

Reactant 4

HCID 5234Sodium ChlorideHCID 24758Sodium hydride2×HCID 139400Triisopropylsilyl chlorideHCID 242087895-(tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo(2,3-b)pyridine

Product 1

HCID 457901505-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridineYield 92%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

3.00 g of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine are suspended in 40 ml of tetrahydrofuran in a flask. 0.73 g of sodium hydride (60% in paraffin oil) are added in portions with ice-cooling. 3.94 ml of chlorotriisopropylsilane is subsequently added dropwise at about 25° C., and the mixture is heated at 40° C. (bath temperature) under nitrogen until the boronic acid ester has reacted completely (HPLC check, about 5 hours). The excess sodium hydride is deactivated using 10 ml of saturated sodium chloride solution. The solvent is removed in vacuo. The residue is diluted with about 50 ml of water and extracted three times with diethyl ether. The combined organic phases are dried over sodium sulfate and purified by means of column chromatography (gradient heptane: EA 5-100% in 15 min.), giving 4.55 g of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-triisopropylsilanyl-1H-pyrrolo[2,3-b]pyridine as white solid (yield 92%, content 92%); MS-FAB (M+H+)=401.2; Rf (nonpolar method): 3.61 min.

Workup

  1. temperaturecooling
  2. customhas reacted completely (HPLC check, about 5 hours)
  3. customThe solvent is removed in vacuo
  4. additionThe residue is diluted with about 50 ml of water
  5. extractionextracted three times with diethyl ether
  6. dry with materialThe combined organic phases are dried over sodium sulfate
  7. custompurified by means of column chromatography (gradient heptane: EA 5-100% in 15 min.)

Sources & evidence

ORD record
ord-0a8319abaf5b473a9b74f6e89430b1d3
Source dataset
uspto-grants-2015_04
Patent number
US09006255B2

Reaction notes

Loading…