Tributyl(1-fluorovinyl)stannane → HCID 86668305, compound

HRID 75099Notes

Reaction equation

HRID 75099 reaction equation
[NH2:1][C:2]1[C:7]([F:8])=[C:6]([Cl:9])[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[C:3]=1I.C([Sn](CCCC)(CCCC)[C:20]([F:22])=[CH2:21])CCC>ClC(Cl)C.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[C:7]([F:8])=[C:6]([Cl:9])[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[C:3]=1[C:20]([F:22])=[CH2:21]

Participants

5

Reactant 2

HCID 11823857Tributyl(1-fluorovinyl)stannaneHCID 86668303Methyl 4-amino-6-chloro-5-fluoro-3-iodopicolinate

Product 1

HCID 86668305HCID 86668305, compoundYield 70.2%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 63651,1-DichloroethaneSolvent

Conditions

Temperature
70 °C

Procedure

Methyl 4-amino-6-chloro-5-fluoro-3-iodopicolinate (0.4 g, 1.210 mmol), tributyl(1-fluorovinyl)stannane (0.608 g, 1.816 mmol), and bis(triphenyl-phosphine)palladium(II) chloride (0.127 g, 0.182 mmol) were combined in dichloroethane (2.4 mL) and stirred at 70° C. overnight. The reaction mixture was concentrated onto celite and purified by flash column chromatography (SiO2, hexanes/EtOAc gradient) to afford the title compound (211 mg, 0.849 mmol, 70.1% yield) as a yellow solid: mp 98-100° C.; 1H NMR (400 MHz, CDCl3) δ 5.28 (dd, J=15.0, 3.6 Hz, 1H), 4.94 (s, 2H), 4.81 (dd, J=47.3, 3.6 Hz, 1H), 3.93 (s, 3H); 19F NMR (376 MHz, CDCl3) δ −89.04, −138.74; ESIMS m/z 249 [(M+H]+).

Workup

  1. concentrationThe reaction mixture was concentrated onto celite
  2. custompurified by flash column chromatography (SiO2, hexanes/EtOAc gradient)

Sources & evidence

ORD record
ord-c7b1c46047ec4fbd983dc4deedf236a0
Source dataset
uspto-grants-2014_09
Patent number
US08835409B2

Reaction notes

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