Triethylamine → 4-(4-Trimethylsilanylethynyl-benzenesulfonyl)-piperazine-1-carboxylic acid tert-butyl ester

HRID 1644724Notes

Reaction equation

HRID 1644724 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].C(N(CC)CC)C.[C:14]([O:18][C:19]([N:21]1[CH2:26][CH2:25][N:24]([S:27]([C:30]2[CH:35]=[CH:34][C:33](Br)=[CH:32][CH:31]=2)(=[O:29])=[O:28])[CH2:23][CH2:22]1)=[O:20])([CH3:17])([CH3:16])[CH3:15]>ClCCl.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:14]([O:18][C:19]([N:21]1[CH2:26][CH2:25][N:24]([S:27]([C:30]2[CH:35]=[CH:34][C:33]([C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])=[CH:32][CH:31]=2)(=[O:29])=[O:28])[CH2:23][CH2:22]1)=[O:20])([CH3:17])([CH3:15])[CH3:16]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 166655764-(4-BOC-piperazinosulfonyl)bromobenzene

Product 1

HCID 593508064-(4-Trimethylsilanylethynyl-benzenesulfonyl)-piperazine-1-carboxylic acid tert-butyl esterYield 115.1%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
50 °C

Procedure

Trimethylsilylacetylene (0.70 mL, 4.94 mmol) and triethylamine (2.80 mL, 19.74 mmol) were added to a stirred solution of 4-(4-bromo-benzenesulfonyl)-piperazine-1-carboxylic acid tert-butyl ester (1.00 g, 2.468 mmol) in dry dichloromethane (12 mL), then the reaction mixture was degassed with argon for 30 minutes at room temperature. To the reaction mixture were added Pd(PPh3)2Cl2 (0.173 g, 0.25 mmol) and CuI (0.047 g, 0.25 mmol), then the reaction mixture was heated at 50° C. for 14 hours under an argon atmosphere. The reaction mixture was cooled to room temperature and then concentrated in vacuo to yield a crude residue, which was dissolved in dichloromethane (20 mL) and washed with water (2×5 mL) and brine (5 mL). The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo to afford a black colored crude product, which was finally purified using silica gel (100-200 mesh) column chromatography (2:23 ethyl acetate-hexanes to 2:18 ethyl acetate in hexanes) to furnish 1.20 g (80%) of 4-(4-trimethylsilanylethynyl-benzenesulfonyl)-piperazine-1-carboxylic acid tert-butyl ester as a brown solid. MS cald. for C20H30N2O4SSi [(M+NH4)+] 440, obsd. 440.0.

Workup

  1. customthe reaction mixture was degassed with argon for 30 minutes at room temperature
  2. temperatureThe reaction mixture was cooled to room temperature
  3. concentrationconcentrated in vacuo
  4. customto yield a crude residue, which
  5. washwashed with water (2×5 mL) and brine (5 mL)
  6. dry with materialThe organic phase was dried over anhydrous sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customto afford a black colored crude product, which
  9. customwas finally purified

Sources & evidence

ORD record
ord-64f97afce59e482588291cf4aa8ba130
Source dataset
uspto-grants-2012_02
Patent number
US08124629B2

Reaction notes

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