Allyltributylstannane → (S)-alpha-[[(1,1-dimethylethoxy)carbonyl]amino]-4-(2-propenyl)benzenepropanoic acid methyl ester

HRID 1721225Notes

Reaction equation

HRID 1721225 reaction equation
[CH3:1][O:2][C:3](=[O:28])[C@@H:4]([NH:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:5][C:6]1[CH:11]=[CH:10][C:9](OS(C(F)(F)F)(=O)=O)=[CH:8][CH:7]=1.[CH2:29]([Sn](CCCC)(CCCC)CCCC)[CH:30]=[CH2:31].[Cl-].[Li+]>CN(C)C=O.CCOCC.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>[CH3:1][O:2][C:3](=[O:28])[C@@H:4]([NH:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:5][C:6]1[CH:11]=[CH:10][C:9]([CH2:31][CH:30]=[CH2:29])=[CH:8][CH:7]=1

Participants

7

Reactant 3

HCID 90628AllyltributylstannaneHCID 433294Lithium ChlorideHCID 10455198(S)-Methyl 2-((tert-butoxycarbonyl)amino)-3-(4-(((trifluoromethyl)sulfonyl)oxy)phenyl)propanoate

Product 1

HCID 14560595(S)-alpha-[[(1,1-dimethylethoxy)carbonyl]amino]-4-(2-propenyl)benzenepropanoic acid methyl esterYield 92.2%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

Argon was passed through a solution of 7.0 g (0.0164 mol) of (S)-4-[[(trifluoromethyl)sulfonyl]oxy]-alpha-[[(1,1-dimethylethoxy)carbonyl]amino]benzenepropanoic acid methyl ester, 5.7 g (0.0165 mol) of allyltributyl tin, and 1.42 g (0.04 mol) of lithium chloride in 50 mL of dimethylformamide for 10 minutes and 210 mg (0.0003 mol) of bis(triphenylphosphine)palladium dichloride was added. The bath temperature was raised to 90°-95° C. for 40 minutes and the mixture was allowed to cool. The mixture was diluted with ether and washed with water and saturated sodium chloride solution and dried over magnesium sulfate. The residue obtained after filtration and evaporation was purified by preparative liquid chromatography using silica gel cartridges on a Waters Prep 500 chromatograph, eluting with 10% ethyl acetate-hexane to give 4.83 g (92%) of (S)-alpha-[[(1,1-dimethylethoxy)carbonyl]amino]-4-(2-propenyl)benzenepropanoic acid methyl ester, mp 56°-59° C.

Workup

  1. temperatureThe bath temperature was raised to 90°-95° C. for 40 minutes
  2. temperatureto cool
  3. washwashed with water and saturated sodium chloride solution
  4. dry with materialdried over magnesium sulfate
  5. customThe residue obtained
  6. filtrationafter filtration and evaporation
  7. customwas purified by preparative liquid chromatography
  8. washeluting with 10% ethyl acetate-hexane

Sources & evidence

ORD record
ord-e89a348f725542e2875f3ee5cb4c817f
Source dataset
uspto-grants-1996_04
Patent number
US05508437

Reaction notes

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