Tris(1,1-dimethylethyl)phosphine → HCID 59807036, compound

HRID 1922453Notes

Reaction equation

HRID 1922453 reaction equation
P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.Br[C:15]1[CH:16]=[C:17]2[C:21](=[CH:22][CH:23]=1)[N:20]([CH:24]1[CH2:28][CH2:27][N:26]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH2:25]1)[CH2:19][CH2:18]2.[Li+].C[Si]([N-:41][Si](C)(C)C)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1.O.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]>[NH2:41][C:15]1[CH:16]=[C:17]2[C:21](=[CH:22][CH:23]=1)[N:20]([CH:24]1[CH2:28][CH2:27][N:26]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH2:25]1)[CH2:19][CH2:18]2

Participants

8

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 2724141Tetrabutylammonium FluorideHCID 2733832Lithium HexamethyldisilazideHCID 59807115HCID 59807115, compound

Product 1

HCID 59807036HCID 59807036, compoundYield 82.3%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
100 °C

Procedure

A suspension of Pd2(dba)3 (0.124 g, 0.136 mmol) and PtBu3 (1.65 mL, 0.544 mmol, 10% wt in hexane) in anhydrous THF (5 mL) was treated with a solution of compound 3 (1.0 g, 2.722 mmol) in THF (15 mL) followed by LiHMDS (5.44 mL, 5.445 mmol, 1 M solution in THF) 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 TBAF (5 mL, 1 M solution in THF) and stirred for 20 min. The reaction was diluted with water (25 mL) and product was extracted into ether (3×30 mL) and the combined organic fractions were dried (Na2SO4) and concentrated to give a dark brown residue. The crude product was purified by column chromatography (2 N NH3 in methanol:CH2Cl2, 3:97) to obtain compound 4 (0.68 g, 82%) as a foam. ESI-MS (m/z, %): 304 (MH+, 16), 248 (100), 134 (25).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. stirringstirred for 20 min
  3. extractionwas extracted into ether (3×30 mL)
  4. dry with materialthe combined organic fractions were dried (Na2SO4)
  5. concentrationconcentrated
  6. customto give a dark brown residue
  7. customThe crude product was purified by column chromatography (2 N NH3 in methanol:CH2Cl2, 3:97)

Sources & evidence

ORD record
ord-ba92a893bbd9407ba1e60b5783dde1b6
Source dataset
uspto-grants-2012_05
Patent number
US08173813B2

Reaction notes

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