Allyltributylstannane → 3-(1-Boc-2-(s)-pyrrolidinylmethoxy)-6-ethenyl-5-methylpyridine

HRID 365913Notes

Reaction equation

HRID 365913 reaction equation
[C:1]([N:8]1[CH2:12][CH2:11][CH2:10][C@H:9]1[CH2:13][O:14][C:15]1[CH:16]=[N:17][C:18](Cl)=[C:19]([CH3:21])[CH:20]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[CH2:23]([Sn](CCCC)(CCCC)CCCC)[CH:24]=C>C1(C)C=CC=CC=1>[C:1]([N:8]1[CH2:12][CH2:11][CH2:10][C@H:9]1[CH2:13][O:14][C:15]1[CH:16]=[N:17][C:18]([CH:23]=[CH2:24])=[C:19]([CH3:21])[CH:20]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2]

Participants

4

Reactant 2

HCID 90628AllyltributylstannaneHCID 229618403-(1-Boc-2-(s)-pyrrolidinylmethoxy)-6-chloro-5-methylpyridine

Product 1

HCID 219714663-(1-Boc-2-(s)-pyrrolidinylmethoxy)-6-ethenyl-5-methylpyridineYield 57%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

3-(1-BOC-2-(S)-pyrrolidinylmethoxy)-6-chloro-5-methylpyridine (830 mg, 2.57 mmol) in toluene (10 mL) was added [1,1'-bis(diphenyl-phosphino)ferrocene]dichloropalladium(U) (83 mg) and allyltributyltin (1.3 mL, 5.1 mmol). The mixture was stirred and refluxed for 16 h. Solvent was evaporated and the residue was chromatographed (silica gel; hexane/EtOAc, 10:1 to 3:2) to afford an oil (450 mg, 57%): 1H NMR (CDCl3, 300 MHz) δ 1.47 (s, 9H), 1.62 (m, 1H), 1.86 (m, 1H), 2.00-2.10 (m, 2H), 2.34 (s, 3H), 3.30-3.46 (m, 2H), 3.90 (m, 1H), 4.04-4.20 (m, 2H), 5.37 (d, 1H, J=11.0 Hz), 6.20 (d, 1H, J=17.0 Hz), 6.94 (dd, 1H, J=11.0, 17.0 Hz), 7.02 (br s, 1H), 8.14 (d, 1H, J=2.5 Hz); MS (CI/NH3) m/z 319 (M+H)+.

Workup

  1. temperaturerefluxed for 16 h
  2. customSolvent was evaporated
  3. customthe residue was chromatographed (silica gel; hexane/EtOAc, 10:1 to 3:2)

Sources & evidence

ORD record
ord-d94d2ea8c9d44a08ba0ee142afa55619
Source dataset
uspto-grants-2000_10
Patent number
US06127386

Reaction notes

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