Tributylvinyltin → 3-(1-BOC-2-(S)-azetidinylmethoxy)-6-ethenylpyridine

HRID 365924Notes

Reaction equation

HRID 365924 reaction equation
[C:1]([N:8]1[CH2:11][CH2:10][C@H:9]1[CH2:12][O:13][C:14]1[CH:15]=[N:16][C:17](Cl)=[CH:18][CH:19]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[CH:21]([Sn](CCCC)(CCCC)CCCC)=[CH2:22]>C1(C)C=CC=CC=1.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]>[C:1]([N:8]1[CH2:11][CH2:10][C@H:9]1[CH2:12][O:13][C:14]1[CH:15]=[N:16][C:17]([CH:21]=[CH2:22])=[CH:18][CH:19]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2]

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 105182243-(1-t-butyloxycarbonyl-(2S)-azetidinylmethoxy)-6-chloropyridine

Product 1

HCID 229618283-(1-BOC-2-(S)-azetidinylmethoxy)-6-ethenylpyridineYield 85%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 1140TolueneSolvent

Procedure

To a solution of 3-(1-BOC-2-(S)-azetidinylmethoxy)-6-chloropyridine (1.8 g, 6.04 mmol) in toluene (25 mL) was added vinyltributyltin (2.7 mL, 9.06 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (180 mg). After heating at reflux for 16 h, the resulting mixture was cooled to room temperature and the solvent was removed. The residue was chromatographed (silica gel; hexane/EtOAc, 10:1) to afford the title compound (1.49 g, 85%): 1H NMR (CDCl3, 300 MHz) δ 1.40 (s, 9H), 2.25-2.30 (m, 2H), 3.85-3.90 (m, 2H), 4.16 (m, 1H), 4.35 (m, 1H), 4.54 (m, 1H), 5.35 (dd, 1H, J=1.0, 12.0 Hz), 6.05 (dd, 1H, J=1.0, 18.0 Hz), 6.80 (dd, 1H, J=12.0, 18.0 Hz), 7.20-7.26 (m, 2H), 8.35 (d, 1H, J=3.0 Hz); MS (CI/NH3) m/z 291 (M+H)+, 319 (M+NH4)+.

Workup

  1. temperatureAfter heating
  2. temperatureat reflux for 16 h
  3. customthe solvent was removed
  4. customThe residue was chromatographed (silica gel; hexane/EtOAc, 10:1)

Sources & evidence

ORD record
ord-4de3b79ddc124abfbb5efbaddd19c4d5
Source dataset
uspto-grants-2000_10
Patent number
US06127386

Reaction notes

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