Acetylene → rac-(E)-5-[2-(3-methoxy-3-oxo-1-propenyl)-3-[6-[(tetrahydro-2H-pyran-2-yl)oxy]-1-hexynyl]phenoxy]pentanoic acid methyl ester

HRID 327998Notes

Reaction equation

HRID 327998 reaction equation
[CH3:1][O:2][C:3](=[O:29])[CH2:4][CH2:5][CH2:6][CH2:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11](OS(C(F)(F)F)(=O)=O)[C:10]=1/[CH:23]=[CH:24]/[C:25]([O:27][CH3:28])=[O:26].[O:30]1[CH2:35][CH2:34][CH2:33][CH2:32][CH:31]1[O:36][CH2:37][CH2:38][CH2:39][CH2:40][C:41]#[CH:42].C(N(CC)CC)C.C#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.C(OCC)(=O)C.O.CN(C)C=O>[CH3:1][O:2][C:3](=[O:29])[CH2:4][CH2:5][CH2:6][CH2:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([C:42]#[C:41][CH2:40][CH2:39][CH2:38][CH2:37][O:36][CH:31]2[CH2:32][CH2:33][CH2:34][CH2:35][O:30]2)[C:10]=1/[CH:23]=[CH:24]/[C:25]([O:27][CH3:28])=[O:26]

Participants

9

Reactant 4

HCID 6326Acetylene2×HCID 8471TriethylamineHCID 2821772-(Hex-5-yn-1-yloxy)tetrahydro-2h-pyranHCID 86747456(E)-5-[3-[[(trifluoromethyl)sulfonyl]oxy]-2-(3-methoxy-3-oxo-1-propenyl)phenoxy]pentanoic acid methyl ester

Product 1

HCID 67780362rac-(E)-5-[2-(3-methoxy-3-oxo-1-propenyl)-3-[6-[(tetrahydro-2H-pyran-2-yl)oxy]-1-hexynyl]phenoxy]pentanoic acid methyl esterYield 38.1%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 2.27 g (5 mmol) of (E)-5-[3-[[(trifluoromethyl)sulfonyl]oxy]-2-(3-methoxy-3-oxo-1-propenyl)phenoxy]pentanoic acid methyl ester, 1.0 g (5.5 mmol) of rac-6-[(tetrahydro-2H-pyran-2-yl)oxy]-1-hexyne, 0.3 g (0.428 mmol) of dichlorobis(triphenylphosphine)palladium (II), 0.075 g of cuprous iodide, 7.5 mL of dry triethylamine, and 35 mL of dry N,N-dimethylforamide was stirred and heated at 100° C. for 3.5 hr. An additional 0.25 g of the acetylene was added and heating was continued for 24 hr at which point 0.75 g of the acetylene was added and heating was continued for 6 hr. The resulting mixture was cooled, poured into water and worked-up with ethyl acetate in the usual manner. The crude, oily product was chromatographed on silica gel. Elution with 10:1 toluene-ethyl acetate afforded 0.9 g (38%) of rac-(E)-5-[2-(3-methoxy-3-oxo-1-propenyl)-3-[ 6-[(tetrahydro-2H-pyran-2-yl)oxy]-1hexynyl]phenoxy]pentanoic acid methyl ester as a yellow oil.

Workup

  1. temperatureheating
  2. additionwas added
  3. temperatureheating
  4. waitwas continued for 6 hr
  5. temperatureThe resulting mixture was cooled
  6. customThe crude, oily product was chromatographed on silica gel
  7. washElution with 10:1 toluene-ethyl acetate

Sources & evidence

ORD record
ord-23629a99c4dc4aa196a2f84073fa4c04
Source dataset
uspto-grants-1993_12
Patent number
US05273999

Reaction notes

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