Potassium Phosphate, Tribasic → HCID 66733871, compound

HRID 2047043Notes

Reaction equation

HRID 2047043 reaction equation
Cl[C:2]1[CH:7]=[C:6]([N:8]([CH2:17][O:18][CH2:19][CH2:20][Si:21]([CH3:24])([CH3:23])[CH3:22])[CH2:9][O:10][CH2:11][CH2:12][Si:13]([CH3:16])([CH3:15])[CH3:14])[N:5]2[N:25]=[CH:26][CH:27]=[C:4]2[N:3]=1.B([O-])[O-].CC1(C)C(C)(C)OB([CH2:39][C:40]2[CH:45]=[CH:44][C:43]([CH2:46][C:47]([O:49][CH3:50])=[O:48])=[CH:42][CH:41]=2)O1.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].O1CCOCC1>[CH3:14][Si:13]([CH3:16])([CH3:15])[CH2:12][CH2:11][O:10][CH2:9][N:8]([CH2:17][O:18][CH2:19][CH2:20][Si:21]([CH3:24])([CH3:23])[CH3:22])[C:6]1[N:5]2[N:25]=[CH:26][CH:27]=[C:4]2[N:3]=[C:2]([CH2:39][C:40]2[CH:41]=[CH:42][C:43]([CH2:46][C:47]([O:49][CH3:50])=[O:48])=[CH:44][CH:45]=2)[CH:7]=1

Participants

8

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 674944814-(2-Methoxy-2-oxoethyl)benzylboronic Acid Pinacol EsterHCID 772312195-chloro-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)pyrazolo[1,5-a]pyrimidin-7-amineHCID 178514824HCID 178514824, compound

Product 1

HCID 66733871HCID 66733871, compound

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

Under Ar, 5-chloro-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)pyrazolo[1,5-a]pyrimidin-7-amine (429 mg, 1.0 mmol) was mixed with Pd(dppf)Cl2 (82 mg, 0.1 mmol, boronate, methyl 2-(4-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)phenyl)acetate (480 mg, 1.65 mmol, not very pure), K3PO4 (424 mg, 2.0 mmol) and dioxane (10 mL). The resulting mixture was heated at 100° C. and stirred over night. After cooled to room temperature, the mixture was diluted with EtOAc (100 mL) and filtered through celite. After concentration, the crude was purified with column (silica gel, 10˜30% EA/hexane) gave the product, methyl 2-(4-((7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)pyrazolo[1,5-a]pyrimidin-5-yl)methyl)phenyl)acetate (188 mg) and recovered the starting material 5-chloro-N,N-bis((2-(trimethylsilyl)ethoxy)methyl)pyrazolo[1,5-a]pyrimidin-7-amine (289 mg). HPLC-MS tR=2.50 min (UV254 nm); mass calculated for formula C28H44N4O4Si2 556.3, observed LCMS m/z 557.3 (M+H).

Workup

  1. temperatureAfter cooled to room temperature
  2. filtrationfiltered through celite
  3. concentrationAfter concentration
  4. customthe crude was purified with column (silica gel, 10˜30% EA/hexane)

Sources & evidence

ORD record
ord-66d99ed100ed465c9353ca43371108b1
Source dataset
uspto-grants-2013_11
Patent number
US08591943B2

Reaction notes

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