(z)-7-{(1r,2s)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-cyclopent-3-enyl}-hept-5-enoic acid methyl ester → (z)-7-{(1r,2r)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-cyclopentyl}-hept-5-enoic acid methyl ester

HRID 250782Notes

Reaction equation

HRID 250782 reaction equation
[CH3:1][O:2][C:3](=[O:36])[CH2:4][CH2:5][CH2:6]/[CH:7]=[CH:8]\[CH2:9][C@H:10]1[C:14](=[O:15])[CH:13]=[CH:12][C@@H:11]1/[CH:16]=[CH:17]/[C@@H:18]([O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30])[CH2:19][CH2:20][C:21]1[S:22][C:23]([CH3:27])=[C:24]([Br:26])[CH:25]=1>C1(C)C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu].[Cu].[Cu].[Cu].[Cu].[Cu]>[CH3:1][O:2][C:3](=[O:36])[CH2:4][CH2:5][CH2:6]/[CH:7]=[CH:8]\[CH2:9][C@H:10]1[C:14](=[O:15])[CH2:13][CH2:12][C@@H:11]1/[CH:16]=[CH:17]/[C@@H:18]([O:28][Si:29]([C:32]([CH3:34])([CH3:33])[CH3:35])([CH3:30])[CH3:31])[CH2:19][CH2:20][C:21]1[S:22][C:23]([CH3:27])=[C:24]([Br:26])[CH:25]=1

Participants

4

Reactant 1

HCID 16655598(z)-7-{(1r,2s)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-cyclopent-3-enyl}-hept-5-enoic acid methyl ester

Product 1

HCID 67092649(z)-7-{(1r,2r)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-cyclopentyl}-hept-5-enoic acid methyl esterYield 89.3%

Reagents, catalysts & solvents 2

HCID 11982471Stryker's reagentCatalystHCID 1140TolueneSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of 7 (170 mg, 0.28 mmol) in 4 mL toluene was added, by cannula, to a −40° C. mixture of hydrido(triphenylphosphine)copper(I) hexamer (300 mg, 0.15 mmol) in 4 mL toluene, rinsing with 0.5 mL toluene. The temperature was allowed to warm to 0° C. over 1 h and then was allowed to warm to room temperature. After a further 1 h, the reaction was quenched by addition of 15 mL saturated NH4Cl solution. The mixture was extracted with ethyl acetate (3×15 mL) and the combined ethyl acetate solution was dried (Na2SO4), filtered and evaporated. Purification by flash chromatography (8% ethyl acetate/hexanes→10%) gave the title ketone (150 mg, 0.25 mmol, 89%).

Workup

  1. washrinsing with 0.5 mL toluene
  2. temperatureto warm to room temperature
  3. customthe reaction was quenched by addition of 15 mL saturated NH4Cl solution
  4. extractionThe mixture was extracted with ethyl acetate (3×15 mL)
  5. dry with materialthe combined ethyl acetate solution was dried (Na2SO4)
  6. filtrationfiltered
  7. customevaporated
  8. customPurification by flash chromatography (8% ethyl acetate/hexanes→10%)

Sources & evidence

ORD record
ord-77695b7535534544b7b7b91a6b56f4e5
Source dataset
uspto-grants-2011_01
Patent number
US07863319B2

Reaction notes

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