Cesium carbonate → HCID 66593803, compound

HRID 1093307Notes

Reaction equation

HRID 1093307 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([O:10][CH2:11][CH2:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[C:6]([CH:9]=1)[C:7]#[N:8].[C:20]([O:24][C:25](=[O:37])[NH:26][C:27]1([C:35]#[CH:36])[CH2:32][O:31][C:30]([CH3:34])([CH3:33])[O:29][CH2:28]1)([CH3:23])([CH3:22])[CH3:21].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.C(=O)([O-])[O-].[Cs+].[Cs+]>C(#N)C.CC#N.CC#N.Cl[Pd]Cl.O>[C:20]([O:24][C:25](=[O:37])[NH:26][C:27]1([C:35]#[C:36][C:2]2[CH:3]=[CH:4][C:5]([O:10][CH2:11][CH2:12][CH2:13][C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)=[C:6]([C:7]#[N:8])[CH:9]=2)[CH2:32][O:31][C:30]([CH3:34])([CH3:33])[O:29][CH2:28]1)([CH3:23])([CH3:22])[CH3:21]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 115143851,1-Dimethylethyl N-(5-ethynyl-2,2-dimethyl-1,3-dioxan-5-yl)carbamateHCID 20987598HCID 20987598, compound

Product 1

HCID 66593803HCID 66593803, compound

Reagents, catalysts & solvents 3

HCID 6093782Bis(acetonitrile)dichloropalladiumCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

Compound 1-1 (0.720 g), (5-ethynyl-2,2-dimethyl-1,3-dioxan-5-yl)carbamic acid t-butyl ester (0.634 g) synthesized according to the known method (e.g., Tetrahedron vol.57 (2001) pages 6531-6538), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (0.050 g), bis(acetonitrile)palladium(II) dichloride (0.009 g) and cesium carbonate (0.855 g) were stirred in acetonitrile (8.7 ml) at 70° C. for 7 hr. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to give (5-{2-[3-cyano-4-(3-phenylpropoxy)phenyl]ethynyl}-2,2-dimethyl-1,3-dioxan-5-yl)carbamic acid t-butyl ester as a pale-brown solid. This solid was dissolved in ethyl acetate (5 ml), 10% palladium carbon (containing water about 50%, 0.044 g) was added, and the mixture was stirred under a hydrogen atmosphere at room temperature for 3 hr. The solution was filtered, and the filtrate was concentrated to give the object product (0.408 g) as a brown oil.

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washwashed with saturated brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. customThe solvent was evaporated under reduced pressure
  5. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-55a68a284d6545c0af75f63989a9d65d
Source dataset
uspto-grants-2012_03
Patent number
US08129361B2

Reaction notes

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