Triphenylphosphine → HCID 10270277, compound

HRID 1860640Notes

Reaction equation

HRID 1860640 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH2:19][C:20]([CH3:26])([CH3:25])[CH2:21][C:22]([OH:24])=[O:23])[CH:5]=[CH:6][C:7]=1[O:8][CH2:9][CH2:10][CH2:11][NH:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][N:14]=1.[C:27]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:28]=1.C[Si](C#C)(C)C>CCN(CC)CC.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>[C:27]([C:2]1[CH:3]=[C:4]([CH2:19][C:20]([CH3:26])([CH3:25])[CH2:21][C:22]([OH:24])=[O:23])[CH:5]=[CH:6][C:7]=1[O:8][CH2:9][CH2:10][CH2:11][NH:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][N:14]=1)#[CH:28]

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 10223945HCID 10223945, compound

Product 1

HCID 10270277HCID 10270277, compoundYield 161.9%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

The final product of EXAMPLE 13, STEP 4 (500 mg) was dissolved in Et3N (10 ml) was treated with Cul (40 mg), triphenylphosphine (80 mg), Pd(Ph3P)2Cl2 (40 mg) and (trimethylsilyl) acetylene (1 ml). The reaction mixture was heated to 120 C. in a sealed tube for 20 hours under nitrogen atmosphere. The mixture was cooled to room temperature and was filtered through celite under vacuum. The filtrate was concentrated. The residue was dissolved in ethyl acetate and was washed with a saturated solution of ammonium chloride and dried over Na2SO4. The solid was removed by filtration and the filtrate was concentrated. The cude product was purified by flash chromatography on silica gel (EtOAc/Hexane/NH4OH: 80/19.5/0.5) to give 181 mg of desired compound as oily gum. NMR spectrum was consistent for the proposed structure.

Workup

  1. temperatureThe reaction mixture was heated to 120 C
  2. filtrationwas filtered through celite under vacuum
  3. concentrationThe filtrate was concentrated
  4. dissolutionThe residue was dissolved in ethyl acetate
  5. washwas washed with a saturated solution of ammonium chloride
  6. dry with materialdried over Na2SO4
  7. customThe solid was removed by filtration
  8. concentrationthe filtrate was concentrated
  9. customThe cude product was purified by flash chromatography on silica gel (EtOAc/Hexane/NH4OH: 80/19.5/0.5)

Sources & evidence

ORD record
ord-937e3f8278424e69b1e4526fa602b260
Source dataset
uspto-grants-2003_03
Patent number
US06531494B1

Reaction notes

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