Tributylvinyltin → N-benzyl-2-chloro-7-vinylthieno[3,2-d]pyrimidin-4-amine

HRID 1485506Notes

Reaction equation

HRID 1485506 reaction equation
[CH2:1]([NH:8][C:9]1[C:10]2[S:18][CH:17]=[C:16](Br)[C:11]=2[N:12]=[C:13]([Cl:15])[N:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:20]([Sn](CCCC)(CCCC)C=C)[CH2:21]CC.[F-].[K+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([NH:8][C:9]1[C:10]2[S:18][CH:17]=[C:16]([CH:20]=[CH2:21])[C:11]=2[N:12]=[C:13]([Cl:15])[N:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 522689Potassium FluorideHCID 86675658N-benzyl-7-bromo-2-chlorothieno[3,2-d]pyrimidin-4-amine

Product 1

HCID 86675661N-benzyl-2-chloro-7-vinylthieno[3,2-d]pyrimidin-4-amineYield 56.2%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

N-Benzyl-7-bromo-2-chlorothieno[3,2-d]pyrimidin-4-amine (200 mg, 0.56 mmol) was dissolved in dioxane (2.5 mL) and nitrogen was flown for 20 minutes. After adding Pd(PPh3)4 (41 mg, 0.036 mmol) and tributyl(vinyl)tin (0.18 mL, 0.62 mmol), the mixture was stirred at 120° C. for 7 hours. The reaction mixture was cooled to room temperature and stirred for 2 hours after adding 10% potassium fluoride aqueous solution (5 mL). The reaction solution was filtered with celite and washed with ethyl acetate. The aqueous layer was separated from the organic layer and extracted once more with ethyl acetate. The combined organic layer was concentrated by drying with MgSO4. Purification of the mixture by silica gel chromatography (DCM/MeOH=97/3) yielded the target compound (95 mg, 55% yield).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. stirringstirred for 2 hours
  3. filtrationThe reaction solution was filtered with celite
  4. washwashed with ethyl acetate
  5. customThe aqueous layer was separated from the organic layer
  6. extractionextracted once more with ethyl acetate
  7. concentrationThe combined organic layer was concentrated
  8. dry with materialby drying with MgSO4
  9. customPurification of the mixture by silica gel chromatography (DCM/MeOH=97/3)

Sources & evidence

ORD record
ord-c04d7e16c94a49778565b2e21027138b
Source dataset
uspto-grants-2016_08
Patent number
US09422307B2

Reaction notes

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