Tributyl(1-fluorovinyl)stannane → Methyl 4-amino-6-chloro-5-fluoro-3-(1-fluorovinyl)picolinate

HRID 75099ノート

反応式

HRID 75099 の反応式
[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]

参加物

5

反応物 2

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

生成物 1

HCID 86668305Methyl 4-amino-6-chloro-5-fluoro-3-(1-fluorovinyl)picolinate収率 70.2%

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 63651,1-Dichloroethane溶媒

反応条件

温度
70 °C

実験手順

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]+).

後処理

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

出典と根拠

ORDレコード
ord-c7b1c46047ec4fbd983dc4deedf236a0
出典データセット
uspto-grants-2014_09
特許番号
US08835409B2

反応ノート

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