tert-Butyl acrylate → HCID 68893121, compound

HRID 1821005Notes

Reaction equation

HRID 1821005 reaction equation
C(P(C(C)(C)C)C1C=CC=C[C:7]=1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)(C)(C)C.C1([CH2:28][NH:29]CC2CCCCC2)CCCCC1.[C:37]([O:41][C:42]([CH3:45])([CH3:44])[CH3:43])(=[O:40])[CH:38]=[CH2:39].[C:46]([C:48]1[CH:49]=[C:50]([C:58]2[S:59]C(C3C=CC(Br)=CC=3C)=N[N:62]=2)[CH:51]=[CH:52][C:53]=1[O:54][CH:55]([CH3:57])[CH3:56])#[N:47]>O1CCOCC1.CCOC(C)=O>[C:46]([C:48]1[CH:49]=[C:50]([C:58]2[S:59][N:29]=[C:28]([C:17]3[CH:16]=[CH:15][C:14]([CH:39]=[CH:38][C:37]([O:41][C:42]([CH3:45])([CH3:44])[CH3:43])=[O:40])=[CH:13][C:12]=3[CH3:7])[N:62]=2)[CH:51]=[CH:52][C:53]=1[O:54][CH:55]([CH3:56])[CH3:57])#[N:47]

Participants

7

Reactant 4

HCID 15458tert-Butyl acrylateHCID 27342152-(Di-tert-butylphosphino)biphenylHCID 4594378Bis(cyclohexylmethyl)amineHCID 69017910HCID 69017910, compound

Product 1

HCID 68893121HCID 68893121, compound

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
95 °C

Procedure

In an oven-dried flask, under an atmosphere of argon, 10 mg of 2-(di-tert-butylphosphino)biphenyl (0.03 mmol) and 13 mg of tris(dibenzylideneacetone)-dipalladium-chloroform complex (0.015 mmol) were dissolved in 10 mL of anhydrous dioxane and the solution was degassed with argon. To this mixture, 100 μL of N,N-dicyclohexylmethylamine (0.45 mmol), 55 μL of tert-butyl acrylate (0.38 mmol), and a dioxane (1 mL) solution of 125 mg (0.30 mmol) of 2-(3-cyano-4-isopropyloxyphenyl)-5-(4-bromo-2-methyphenyl)-1,3,4-thiadiazole (from Step B) were added sequentially via syringe. The resulting mixture was heated under argon atmosphere at 95° C. for 2 h. The reaction mixture was diluted with 20 mL of EtOAc, filtered trough a disposable frit and concentrated. Pure product was isolated by a column chromatography, using Biotage 40S column (eluent: hexanes/EtOAc=4/1) as a mixture of (E)- and (Z)-stereoisomers: 1H NMR (500 MHZ, CDCl3, major, (E)-stereoisomer) δ 1.46 (d, J=6.5, 6H), 2.69 (s, 3H), 4.79 (sep, J=6.5, 1H), 6.47 (d, J=15.5, 1H), 7.12 (d, J=9.0, 1H), 7.51 (d, J=9.0, 1H), 7.52 (s, 1H), 7.61 (d, J=15.5, 1H), 7.80 (d, J=8.0, 1H), 8.18 (d, J=2.0, 1H), 8.25 (dd, J=8.0, 2.0, 1H).

Workup

  1. customthe solution was degassed with argon
  2. filtrationfiltered trough a disposable frit
  3. concentrationconcentrated
  4. customPure product was isolated by a column chromatography

Sources & evidence

ORD record
ord-3a048523913142558faa3b4f0ec15190
Source dataset
uspto-grants-2009_10
Patent number
US07605171B2

Reaction notes

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