Tributylvinyltin → HCID 22961823, compound

HRID 2185730Notes

Reaction equation

HRID 2185730 reaction equation
Br[C:2]1[CH:3]=[C:4]([O:9][CH2:10][C@@H:11]2[CH2:14][CH2:13][N:12]2[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH:5]=[N:6][C:7]=1[Cl:8].[CH:22]([Sn](CCCC)(CCCC)CCCC)=[CH2:23]>C1(C)C=CC=CC=1.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>[Cl:8][C:7]1[C:2]([CH:22]=[CH2:23])=[CH:3][C:4]([O:9][CH2:10][C@@H:11]2[CH2:14][CH2:13][N:12]2[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[CH:5][N:6]=1

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 228726673-(1-BOC-2-(S)-azetidinylmethoxy)-5-bromo-6-chloropyridine

Product 1

HCID 22961823HCID 22961823, compoundYield 84%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
95 °C

Procedure

To 5-bromo-6-chloro-3-(1-t-butyloxycarbonyl-2-(S)-azetidinylmethoxy)pyridine from Example 17 above (1.00 g, 2.65 mmol) in toluene (30 mL) was added tetrakis(triphenylphosphine)palladium(0) (93 mg, 0.081 mmol) and vinyltributyltin (0.93 mL, 3.18 mmol). The mixture heated at 95° C. overnight, then the volatile components were removed in vacuo. The residue was chromatographed (silica gel; CH2Cl2/MeOH, 100:2) to afford 2-chloro-3-vinyl-5-(1-t-butyloxycarbonyl-(2S)-azetidinylmethoxy)pyridine as an oil (720 mg, 84%): 1H NMR (CDCl3, 300 MHz) δ1.42 (s, 9H), 2.33 (m, 2H), 3.89 (t, J=8.5 Hz, 2H), 4.14 (m, 1H), 4.36 (m, 1H), 4.52 (m, 1H), 5.50 (d, J=10.9 Hz, 1H), 5.80 (d, J=17 Hz, 1H), 6.98 (dd, J=17.6 Hz, J=11.2 Hz, 1H), 7.44 (d, J=2.7 Hz, 1H), 8.02 (d, J=2.7 Hz, 1H); MS (CI/NH3) m/z: 325 (M+H)+. This product was treated with TFA in CH2Cl2 to give, following extractive work-up, the free base of the title compound. The free amine was converted to the hydrochloride salt by treatment with a solution of HCl in diethyl ether to give the title compound as a light yellow hygroscopic solid: mp 121° C. (dec); MS (CI/NH3): m/z 225 (M+H+), 242 (M+NH4+). Anal. Calcd for C11H13ClN2O.1.1 HCl: C, 49.90; H, 5.37; N, 10.58. Found: C, 49.84; H, 5.25; N, 10.27.

Workup

  1. customthe volatile components were removed in vacuo
  2. customThe residue was chromatographed (silica gel; CH2Cl2/MeOH, 100:2)

Sources & evidence

ORD record
ord-f6560fb242564f7e8ed30e0d2a78d9de
Source dataset
uspto-grants-2002_06
Patent number
US06403575B1

Reaction notes

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