Tri(butyl)vinyltin → HCID 90281270, compound

HRID 1471651Notes

Reaction equation

HRID 1471651 reaction equation
Br[C:2]1[N:10]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[C:9]2[C:4](=[N:5][C:6]([O:18][CH3:19])=[CH:7][CH:8]=2)[C:3]=1[CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22].[CH2:26](C([Sn])=C(CCCC)CCCC)[CH2:27]CC>CN(C=O)C.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>[CH2:24]([O:23][C:21](=[O:22])[CH2:20][C:3]1[C:4]2=[N:5][C:6]([O:18][CH3:19])=[CH:7][CH:8]=[C:9]2[N:10]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[C:2]=1[CH:26]=[CH2:27])[CH3:25]

Participants

5

Reactant 2

HCID 53438229Tri(butyl)vinyltinHCID 90167983HCID 90167983, compound

Product 1

HCID 90281270HCID 90281270, compoundYield 66.6%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
85 °C

Procedure

Under a nitrogen atmosphere, tert-butyl 2-bromo-3-(2-ethoxy-2-oxoethyl)-5-methoxy-1H-pyrrolo[3,2-b]pyridine-1-carboxylate (207 mg, 0.5 mmol), tributylvinyl tin (175 μL, 0.6 mmol) and tetrakis(triphenylphosphine)palladium(0) (29 mg, 0.025 mmol) were combined in 10 mL of DMF, and the mixture was heated to 85° C. overnight. The reaction was allowed to cool to ambient temperature and was partitioned between ethyl acetate and water. The organic layer was separated and washed with 5% aqueous LiCl and brine. The organic layer was then dried over MgSO4, filtered and concentrated to afford crude product which was purified by RP HPLC eluting with acetonitrile and water to afford 120 mg of tert-butyl 3-(2-ethoxy-2-oxoethyl)-5-methoxy-2-vinyl-1H-pyrrolo[3,2-b]pyridine-1-carboxylate. MS (m/z): 361.2 [M+H]+; HPLC retention time 4.69 min (5-99% acetonitrile:water with 0.05% formic acid).

Workup

  1. temperatureto cool to ambient temperature
  2. customwas partitioned between ethyl acetate and water
  3. customThe organic layer was separated
  4. washwashed with 5% aqueous LiCl and brine
  5. dry with materialThe organic layer was then dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto afford crude product which
  9. customwas purified by RP HPLC
  10. washeluting with acetonitrile and water

Sources & evidence

ORD record
ord-44e065365c8d44a09d0a55072f8c8c27
Source dataset
uspto-grants-2015_04
Patent number
US09012441B2

Reaction notes

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