Tributylvinyltin → HCID 22961823, compound

Participants

Reaction Conditions

Reaction Steps

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.

Provenance & Evidence