Allyltributylstannane → 5-Allyl-3-(1-boc-2-(s)-azetidinylmethoxy)-6-chloropyridine

HRID 2305182Notes

Reaction equation

HRID 2305182 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:21])=[C:18](Br)[CH:19]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[CH2:22]([Sn](CCCC)(CCCC)CCCC)[CH:23]=[CH2:24]>C1(C)C=CC=CC=1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:24]([C:18]1[CH:19]=[C:14]([O:13][CH2:12][C@@H:9]2[CH2:10][CH2:11][N:8]2[C:1]([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2])[CH:15]=[N:16][C:17]=1[Cl:21])[CH:23]=[CH2:22]

Participants

5

Reactant 2

HCID 90628AllyltributylstannaneHCID 228726673-(1-BOC-2-(S)-azetidinylmethoxy)-5-bromo-6-chloropyridine

Product 1

HCID 229618845-Allyl-3-(1-boc-2-(s)-azetidinylmethoxy)-6-chloropyridineYield 83.5%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Procedure

3-(1-BOC-2-(S)-Azetidinylmethoxy)-5-bromo-6-chloropyridine (1.0 g, 2.65 mmol) in toluene (10 mL) was added tetrakis(triphenylphosphine) palladium (100 mg) and allyltributyltin (0.99 mL, 3.18 mmol). The mixture was stirred and refluxed for two days. Solvent was evaporated and the residue was chromatographed (silica gel; hexane/EtOAc, 5:1 to 1:1) to afford an oil (750 mg, 83%): 1H NMR (CDCl3, 300 MHz) δ 1.42 (s, 9H), 2.20-2.40 (m, 2H), 3.43 (d, 2H, J=6.5 Hz), 3.88 (t, 2H, J=7.0 Hz), 4.12 (m, 1H), 4.30 (m, 1H), 4.50 (m, 1H), 5.10-5.20 (m, 2H), 5.92 (m, 1H), 7.18 (d, J=3.0 Hz), 7.98 (d, 1H, J=3.0 Hz); MS (CI/NH3) m/z 339 (M+H)+.

Workup

  1. temperaturerefluxed for two days
  2. customSolvent was evaporated
  3. customthe residue was chromatographed (silica gel; hexane/EtOAc, 5:1 to 1:1)

Sources & evidence

ORD record
ord-fa8c3028abce40c8b6b47b9bcaad97ef
Source dataset
uspto-grants-2002_08
Patent number
US06437138B1

Reaction notes

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