Hydrochloric Acid → HCID 59807053, compound

HRID 1922426Notes

Reaction equation

HRID 1922426 reaction equation
P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.Br[C:15]1[CH:32]=[CH:31][C:18]2[N:19]([CH:24]3[CH2:29][CH2:28][N:27]([CH3:30])[CH2:26][CH2:25]3)[CH2:20][CH2:21][CH2:22][CH2:23][C:17]=2[CH:16]=1.[Li+].C[Si]([N-:38][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]>[CH3:30][N:27]1[CH2:28][CH2:29][CH:24]([N:19]2[CH2:20][CH2:21][CH2:22][CH2:23][C:17]3[CH:16]=[C:15]([NH2:38])[CH:32]=[CH:31][C:18]2=3)[CH2:25][CH2:26]1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 2733832Lithium HexamethyldisilazideHCID 59807130HCID 59807130, compound

Product 1

HCID 59807053HCID 59807053, compoundYield 84.7%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
100 °C

Procedure

A suspension of Pd2(dba)3 (70 mg, 0.077 mmol) and PtBu3 10% wt in hexanes (0.94 m/L, 0.31 mmol) in THF (5.0 mL) was treated with a solution of compound 4 (500.0 mg, 1.55 mmol) in THF (5.0 mL) followed by LiHMDS 1 M in THF (3.1 mL, 3.1 mmol) at room temperature. The resulting brown mixture was stirred at 100° C. for 2 hours then cooled to room temperature and treated with 1 N HCl (10 mL) and stirred for 15 minutes. The mixture was basified with 1 N NaOH (25 mL) and extracted with CH2Cl2 (2×100 mL). The combined organic fractions were washed with brine (100 mL), dried (Na2SO4) and concentrated to give a dark brown residue. The crude product was purified by flash chromatography on silica gel (MeOH:CH2Cl2, 5:95 followed by 2 N NH3 in MeOH:CH2Cl2, 5:95) to give compound 5 (339.6 mg, 84.7%) as a dark viscous oil.

Workup

  1. temperaturethen cooled to room temperature
  2. stirringstirred for 15 minutes
  3. extractionextracted with CH2Cl2 (2×100 mL)
  4. washThe combined organic fractions were washed with brine (100 mL)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. customto give a dark brown residue
  8. customThe crude product was purified by flash chromatography on silica gel (MeOH:CH2Cl2, 5:95 followed by 2 N NH3 in MeOH:CH2Cl2, 5:95)

Sources & evidence

ORD record
ord-101a6f47de4948cd929d0fa499af730e
Source dataset
uspto-grants-2012_05
Patent number
US08173813B2

Reaction notes

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