Tributylvinyltin → HCID 86710146, compound

HRID 1051145Notes

Reaction equation

HRID 1051145 reaction equation
[C:1](=[O:33])([O:7][C:8]1[C:13](I)=[C:12]([CH3:15])[N:11]=[C:10]([CH3:16])[C:9]=1[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[O:2][C:3]([CH3:6])([CH3:5])[CH3:4].[Cl-].[Li+].[CH2:36]([Sn](CCCC)(CCCC)C=C)[CH2:37]CC>O1CCOCC1.C(Cl)(Cl)Cl.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>[C:1](=[O:33])([O:7][C:8]1[C:13]([CH:36]=[CH2:37])=[C:12]([CH3:15])[N:11]=[C:10]([CH3:16])[C:9]=1[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[O:2][C:3]([CH3:6])([CH3:5])[CH3:4]

Participants

7

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 70818720HCID 70818720, compound

Product 1

HCID 86710146HCID 86710146, compoundYield 27%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 6212ChloroformSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 8 (85 mg, 0.864 mmol) in 1,4-dioxane (4 ml) were added lithium chloride (73.2 mg, 1.73 mmol), tetrakis(triphenylphosphine)palladium (99.8 mg, 10 mol %) and tributyl(vinyl)tin (0.327 ml, 1.12 mmol). The mixture was heated at reflux for 3 h then cooled and diluted with CHCl3. The mixture was washed with brine, dried over Na2SO4, filtered, and concentrated in under diminished pressure. The residue was purified by column chromatography on silica gel [AcOEt/MeOH (20:1)] to afford tert-butyl 3-hexadecyl-2,6-dimethyl-5-vinylpyridin-4-yl carbonate (10) (19 mg, 27%). 1H NMR (CDCl3) δ 0.02-0.03 (m, 3H), 1.20-1.27 (m, 28H), 1.46 (s, 9H), 2.45 (s, 3H), 2.48 (s, 3H), 2.54-2.56 (m, 2H), 5.55 (dd, 2H, J=17.6 Hz, 11.6 Hz) and 6.50 (dd, 1H, J=11.2 Hz, 11.2 Hz).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 3 h
  3. temperaturethen cooled
  4. washThe mixture was washed with brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in under diminished pressure
  8. customThe residue was purified by column chromatography on silica gel [AcOEt/MeOH (20:1)]

Sources & evidence

ORD record
ord-f00537cdb5444b6182e3261a00794f6f
Source dataset
uspto-grants-2016_07
Patent number
US09388163B2

Reaction notes

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