Tris(1,1-dimethylethyl)phosphine → HCID 59807117, compound

HRID 1922422Notes

Reaction equation

HRID 1922422 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[CH2:29][CH2:28][N:27]([CH3:30])[CH2:26][CH2:25]1)[CH2:19][CH2:18]2.[Li+].C[Si]([N-:36][Si](C)(C)C)(C)C>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:20]2[C:21]3[C:17](=[CH:16][C:15]([NH2:36])=[CH:23][CH:22]=3)[CH2:18][CH2:19]2)[CH2:25][CH2:26]1

Participants

6

Reactant 3

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 2733832Lithium HexamethyldisilazideHCID 21029604HCID 21029604, compound

Product 1

HCID 59807117HCID 59807117, compoundYield 36%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
100 °C

Procedure

Pd2(dba)3 (0.077 g, 0.084 mmol) in dry THF (3 mL) was treated with PtBu3 (1.04 mL, 0.338 mmol, 10% wt in hexanes) at room temperature. The mixture was treated with compound 3 (0.5 g, 1.693 mmol) in dry THF (7 mL) followed by LiHMDS (3.4 mL, 3.387 mmol, 1 M solution in THF) and the resulting mixture was stirred at 100° C. (sealed tube) for 2 h. The reaction was brought to room temperature, quenched with 1 N HCl solution (10 mL) and stirred for 10 min. The solution was made basic with 1 N NaOH solution (50 mL) and product was extracted into ethyl acetate (2×25 mL). The combined ethyl acetate layer was washed with brine (15 mL) and dried (Na2SO4). Solvent was evaporated and crude was purified by column chromatography on silica gel (2 M NH3 in MeOH:CH2Cl2, 2:98 to 5:95) to obtain compound 4 (0.14 g, 36%) as a foam that was used directly in the next step.

Workup

  1. custom(sealed tube) for 2 h
  2. customwas brought to room temperature
  3. customquenched with 1 N HCl solution (10 mL)
  4. stirringstirred for 10 min
  5. extractionwas extracted into ethyl acetate (2×25 mL)
  6. washThe combined ethyl acetate layer was washed with brine (15 mL)
  7. dry with materialdried (Na2SO4)
  8. customSolvent was evaporated
  9. customcrude was purified by column chromatography on silica gel (2 M NH3 in MeOH:CH2Cl2, 2:98 to 5:95)

Sources & evidence

ORD record
ord-1329c08371b6427ca1ebdd0bde1beb53
Source dataset
uspto-grants-2012_05
Patent number
US08173813B2

Reaction notes

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