Ethyl cyclopentanecarboxylate → HCID 10253447, compound

HRID 367325Notes

Reaction equation

HRID 367325 reaction equation
[C:1]1([C:7]2[CH:32]=[CH:31][C:10]([CH2:11][CH:12]3[C:21](=[O:22])[C:20]4[C:15](=[CH:16][C:17](OS(C(F)(F)F)(=O)=O)=[CH:18][CH:19]=4)[O:14][CH2:13]3)=[CH:9][CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C1(C2C=CC=CC=2)C(C=O)=CC=CC=1.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[CH:69]1([C:74]([O:76][CH2:77][CH3:78])=[O:75])[CH2:73][CH2:72][CH2:71][CH2:70]1>CN(C)C=O.C(COC)OC.O.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl.[Cl-].[Zn+2].[Cl-]>[C:1]1([C:7]2[CH:32]=[CH:31][C:10]([CH2:11][CH:12]3[C:21](=[O:22])[C:20]4[C:15](=[CH:16][C:17]([C:69]5([C:74]([O:76][CH2:77][CH3:78])=[O:75])[CH2:73][CH2:72][CH2:71][CH2:70]5)=[CH:18][CH:19]=4)[O:14][CH2:13]3)=[CH:9][CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

10

Reactant 4

HCID 79550Ethyl cyclopentanecarboxylateHCID 80271Tri-o-tolylphosphineHCID 121052(1,1'-Biphenyl)-2-carboxaldehydeHCID 10322097HCID 10322097, compound

Product 1

HCID 10253447HCID 10253447, compound

Reagents, catalysts & solvents 5

HCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 3007855ZincchlorideCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

3-(4-Phenyl-benzyl)-7-trifluoromethylsulfonyloxy-4-chromanone (35.0 g, 91.0 mmole, prepared from the product of Example 2C with biphenyl aldehyde using the procedures of Example 2D and Example 2E, was dissolved in a mixture of dimethylformamide (230 mL) and dimethoxyethane (230 mL). To this solution was added in the following order, tris(2-methylphenyl)phosphine (7.48 g, 24.6 mmole), bis(benzonitrile)palladium (II) chloride (2.44 g, 6.37 mmole), the trimethylsilyl ketene acetal of ethyl cyclopentanecarboxylate (29.26 g, 136.5 mmole), and a 1.0M ethereal solution of zinc chloride (25 mL, 25 mmole). The resulting clear yellow solution was refluxed for about 1 hour. Additional trimethylsilyl ketene acetal (9.75 g, 45.5 mmole) was added at this point and the reflux continued for about another 1 hour. The cooled mixture was diluted with water (1 L) and extracted with ether. The combined ether extracts were washed with water (1 L) and then dried over magnesium sulfate. Filtration and concentration of the extract gave a yellow oil which was chromatographed on silica gel (8:92 ethyl acetate/hexane). This yielded 22.13 g (64%) of the title compound of this Example 5A as a white solid; m.p. 50-56 ° C.; 1H NMR (CDCl3): 1.23 (3H, t, J=7.0), 1.75 (4H, m), 1.9 (2H, m), 2.6 (2H, m), 2.70 (1H, dd, J=10.5, 13.8), 2.9 (1H, m), 3.26 (1H, dd, J=4.3, 13.8), 4.08 (2H, d, J=7.0), 4.15 (1H, dd, J=8.2, 11.5), 4.35 (dd, J=4.3, 11.5), 6.95 (1H, d, J=1.7), 7.02 (1H, dd, J=1.7, 8.3), 7.2-7.4 (5H, m) 7.84 (1H, d, J=8.3).

Workup

  1. temperatureThe resulting clear yellow solution was refluxed for about 1 hour
  2. customcontinued for about another 1 hour
  3. extractionextracted with ether
  4. washThe combined ether extracts were washed with water (1 L)
  5. dry with materialdried over magnesium sulfate
  6. filtrationFiltration and concentration of the extract
  7. customgave a yellow oil which
  8. customwas chromatographed on silica gel (8:92 ethyl acetate/hexane)

Sources & evidence

ORD record
ord-94f1456d130847a0913b3764ac8c0637
Source dataset
uspto-grants-2000_10
Patent number
US06133286

Reaction notes

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