Phenylacetylene → HCID 68470303, compound

HRID 505827Notes

Reaction equation

HRID 505827 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[S:5][C:6]=1[NH:7][C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9].CCN(C(C)C)C(C)C.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.[C:42]1([C:48]#[CH:49])[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1>CCOC(C)=O.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl.[Cu]I>[C:11]([O:10][C:8]([NH:7][C:6]1[S:5][C:4]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:3][C:2]=1[C:49]#[C:48][C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1)=[O:9])([CH3:14])([CH3:13])[CH3:12]

Participants

8

Reactant 4

HCID 10821PhenylacetyleneHCID 81531DiisopropylethylamineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 25258090HCID 25258090, compound

Product 1

HCID 68470303HCID 68470303, compoundYield 96%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Pd(PhCN)2Cl2 (0.03 eq.) and CuI (0.02 eq.) were added to a dry septum-capped vial, which was then sparged with argon and charged with ethyl 4-bromo-5-[(tert-butoxycarbonyl)amino]thiophene-2-carboxylate (prepared as described in example 14, step 4) (1 M solution in dioxane), DIEA (1.2 eq.), P(t-Bu)3 (0.06 eq., 0.8 M solution in dioxane) and phenylacetylene (1.2 eq.). The reaction was stirred overnight at RT, then diluted with AcOEt and filtered trough a small pad of silica gel. The filtrate was concentrated giving a residue that was purified by flash chromatography on silica gel (1:5 AcOEt/petroleum ether) to afford the title compound (96%) as a solid.

Workup

  1. customseptum-capped vial
  2. customwhich was then sparged with argon
  3. filtrationfiltered trough a small pad of silica gel
  4. concentrationThe filtrate was concentrated
  5. customgiving a residue that
  6. customwas purified by flash chromatography on silica gel (1:5 AcOEt/petroleum ether)

Sources & evidence

ORD record
ord-4ac469ca2196431a933140ff862bf342
Source dataset
uspto-grants-2010_08
Patent number
US07781431B2

Reaction notes

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