Potassium Carbonate → 2-(2-Methylpropenyl)-6-vinylisonicotinic acid tert-butyl ester

HRID 1908731Notes

Reaction equation

HRID 1908731 reaction equation
[C:1]([O:5][C:6](=[O:15])[C:7]1[CH:12]=[C:11](Cl)[N:10]=[C:9](Cl)[CH:8]=1)([CH3:4])([CH3:3])[CH3:2].B1(C=C)OB([CH:22]=[CH2:23])OB(C=C)O1.[CH:28]1[CH:33]=[CH:32]N=CC=1.[C:34]([O-])([O-])=O.[K+].[K+]>COCCOC.[OH-].[Na+].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.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]([O:5][C:6](=[O:15])[C:7]1[CH:12]=[C:11]([CH:22]=[CH2:23])[N:10]=[C:9]([CH:34]=[C:33]([CH3:32])[CH3:28])[CH:8]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 3

HCID 11430Potassium CarbonateHCID 27348062,4,6-Trivinylboroxin-Pyridine ComplexHCID 22594123tert-Butyl 2,6-dichloropyridine-4-carboxylate

Product 1

HCID 670271162-(2-Methylpropenyl)-6-vinylisonicotinic acid tert-butyl ester

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolventHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
45 °C

Procedure

To a solution of 2,6-dichloro-isonicotinic acid tert.-butyl ester (500 mg, 2.02 mmol), and 2,4,6-trivinylcyclotriboroxane pyridine complex (170 mg, 0.706 mmol) in DME (12 mL), a solution of 2 M aq. K2CO3 (3 mL) followed by Pd(PPh3)4 (30 mg, 0.041 mmol) and triphenylphosphine (50 mg, 0.187 mmol) is added. The mixture is stirred at 45° C. for 15 h. 2,4,6-Tri-(2-methyl-propenyl)-cycloboroxane pyridine complex (594 mg, 1.83 mmol) is then added to the mixture and stirring is continued at 100° C. for 15 h. The mixture is cooled to rt, diluted with 1 N aq. NaOH solution and extracted twice with diethyl ether. The org. extracts are washed with 1 N aq. NaOH solution (2×30 mL), and brine, dried over Na2SO4, filtered and evaporated. The remaining residue is purified by CC on silica gel eluting with heptane:EA 5:1 to give 2-(2-methyl-propenyl)-6-vinyl-isonicotinic acid tert-butyl ester (780 mg) as a colourless oil containing 2,6-di-(2-methyl-propenyl)-isonicotinic acid tert.-butyl ester as impurity; LC-MS: tR=1.01 min, [M+1]+=260.14.

Workup

  1. additionis added
  2. addition2,4,6-Tri-(2-methyl-propenyl)-cycloboroxane pyridine complex (594 mg, 1.83 mmol) is then added to the mixture
  3. stirringstirring
  4. waitis continued at 100° C. for 15 h
  5. temperatureThe mixture is cooled to rt
  6. extractionextracted twice with diethyl ether
  7. washextracts are washed with 1 N aq. NaOH solution (2×30 mL), and brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. customevaporated
  11. customThe remaining residue is purified by CC on silica gel eluting with heptane:EA 5:1

Sources & evidence

ORD record
ord-fdcfae6497c344649d125aeb76291cb8
Source dataset
uspto-grants-2013_12
Patent number
US08598208B2

Reaction notes

Loading…