Tributylvinyltin → Methyl 4-amino-3-methoxy-6-vinylpicolinate

HRID 407243Notes

Reaction equation

HRID 407243 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6](Br)[N:5]=[C:4]([C:9]([O:11][CH3:12])=[O:10])[C:3]=1[O:13][CH3:14].[CH2:15]([Sn](CCCC)(CCCC)C=C)[CH2:16]CC>ClCCCl.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH2:1][C:2]1[CH:7]=[C:6]([CH:15]=[CH2:16])[N:5]=[C:4]([C:9]([O:11][CH3:12])=[O:10])[C:3]=1[O:13][CH3:14]

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 21696668Methyl 4-amino-6-bromo-3-methoxypicolinate

Product 1

HCID 86675413Methyl 4-amino-3-methoxy-6-vinylpicolinateYield 33%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 111,2-DichloroethaneSolvent

Procedure

Methyl 4-amino-6-bromo-3-methoxypicolinate (1 g, 3.83 mmol), tributyl(vinyl)stannane (1.822 g, 5.75 mmol) and bis(triphenylphosphine)palladium(II) chloride (0.403 g, 0.575 mmol) in DCE (12.77 ml) were stirred at 70° C. overnight. The mixture was adsorbed onto celite and purified by flash column chromatography (ISCO, SiO2 40 g, hexane/EtOAc 100:0 to 0:100 gradient) to afford methyl 4-amino-3-methoxy-6-vinylpicolinate (263 mg, 1.263 mmol, 33% yield) as a yellow oil. EIMS m/z 208; 1H NMR (400 MHz, CDCl3) δ 6.86 (s, 1H), 6.71 (dd, J=17.6, 10.9 Hz, 1H), 5.98 (dd, J=17.6, 1.0 Hz, 1H), 5.42 (dd, J=10.9, 1.0 Hz, 1H), 4.45 (s, 2H), 3.97 (s, 3H), 3.87 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 165.94, 152.06, 148.02, 143.34, 141.60, 136.73, 118.02, 108.63, 61.49, 52.84.

Workup

  1. custompurified by flash column chromatography (ISCO, SiO2 40 g, hexane/EtOAc 100:0 to 0:100 gradient)

Sources & evidence

ORD record
ord-e3670bd5a3e6491a8aa72280debc2cc4
Source dataset
uspto-grants-2014_06
Patent number
US08754229B2

Reaction notes

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