Hydrochloric Acid → HCID 59807098, compound

HRID 1922447Notes

Reaction equation

HRID 1922447 reaction equation
P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.Br[C:15]1[CH:31]=[CH:30][C:18]2[N:19]([CH:24]3[CH2:28][CH2:27][N:26]([CH3:29])[CH2:25]3)[CH2:20][CH2:21][CH2:22][CH2:23][C:17]=2[CH:16]=1.[Li+].C[Si]([N-:37][Si](C)(C)C)(C)C.Cl.[OH-].[Na+]>C1COCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:29][N:26]1[CH2:27][CH2:28][CH:24]([N:19]2[CH2:20][CH2:21][CH2:22][CH2:23][C:17]3[CH:16]=[C:15]([NH2:37])[CH:31]=[CH:30][C:18]2=3)[CH2:25]1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 2733832Lithium HexamethyldisilazideHCID 59807081HCID 59807081, compound

Product 1

HCID 59807098HCID 59807098, compoundYield 94.1%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
100 °C

Procedure

A suspension of Pd2(dba)3 (105 mg, 0.11 mmol) and PtBu3 (10% wt in hexanes, 1.40 mL, 0.46 mmol) in anhydrous THF (5 mL) was treated with a solution of compound 5 (713 mg, 2.30 mmol) in THF (10 mL) followed by LiHMDS (1 M in THF, 4.6 mL, 4.60 mmol) at room temperature. The resulting dark brown mixture was heated to 100° C. and stirred for 3 hours in a sealed tube. The reaction mixture was cooled to room temperature and treated with 1 N HCl (20 mL) and stirred for 15 min, then basified with 1 N NaOH (50 mL). The product was extracted into CH2Cl2 (2×50 mL) and the combined organic fractions were washed with brine (25 mL), dried (MgSO4), filtered and concentrated to give a dark brown residue. The crude product was purified by column chromatography (2 N NH3 in MeOH:CH2Cl2, 5:95) to give compound 6 (531 mg, 94%) as a syrup.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. stirringstirred for 15 min
  3. extractionThe product was extracted into CH2Cl2 (2×50 mL)
  4. washthe combined organic fractions were washed with brine (25 mL)
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give a dark brown residue
  9. customThe crude product was purified by column chromatography (2 N NH3 in MeOH:CH2Cl2, 5:95)

Sources & evidence

ORD record
ord-1bc1a61e64994df59efdd29430f913a9
Source dataset
uspto-grants-2012_05
Patent number
US08173813B2

Reaction notes

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