Tributylphosphine → HCID 131717030, compound

HRID 345234Notes

Reaction equation

HRID 345234 reaction equation
[CH2:1](C(CC(OC)(C)CCCC)=C(O[SiH](C)C)[Sn](CCCC)(CCCC)CCCC)CCC.C([Li])CCC.C(P(CCCC)CCCC)CCC.C(C1CC(=O)C(CCCCCCC(OC)=O)=C1O[SiH](C)C)CCC.[CH2:75]([C:79]([O:105][SiH:106]([CH3:108])[CH3:107])([CH2:84][CH2:85][CH2:86][CH2:87][CH2:88][C@@H:89]1[C@@H:93]([CH:94]=[CH:95][CH2:96][CH:97]([O:102][CH3:103])[CH2:98][CH2:99][CH2:100][CH3:101])[CH2:92][CH2:91][C:90]1=[O:104])[C:80]([O:82][CH3:83])=[O:81])[CH2:76][CH2:77][CH3:78]>C1COCC1.CCCCCC.[Cu]I.C(O)(=O)C>[CH2:75]([C:79]([O:105][SiH:106]([CH3:107])[CH3:108])([CH2:84][CH2:85][CH2:86][CH2:87][CH2:88][C@@H:89]1[C@@H:93]([CH:94]=[CH:95][CH2:96][C:97]([CH3:1])([O:102][CH3:103])[CH2:98][CH2:99][CH2:100][CH3:101])[CH2:92][CH2:91][C:90]1=[O:104])[C:80]([O:82][CH3:83])=[O:81])[CH2:76][CH2:77][CH3:78]

Participants

10

Reactant 5

HCID 13831TributylphosphineHCID 131717031HCID 131717031, compoundHCID 131717032HCID 131717032, compoundHCID 131717033HCID 131717033, compoundHCID 178418339Butyllithium

Product 1

HCID 131717030HCID 131717030, compound

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of (3R,4R)3-t.butyldimethylsilyloxy-4-methoxy-4-methyl-l-tributylstannyl-l-octene 2 (0.58 g, 1 mmol) in THF (1 ml) was treated at -78° C. under nitrogen with n-butyllithium (0.65 ml, 1.6 M in hexane), stirred for 10 min at -78° C. and a solution of copper (I) iodide (0.19 g, 1 mmol) and tri-n-butyl phosphine (0.65 ml, 2.6 mmol) in 1 ml of THF was added. The reaction mixture was warmed to -40° C. and stirred for 1 h when a solution of the (3R)3-t.butyldimethylsilyloxy-5-oxo-l-cyclopenteneheptanoic acid, methyl ester (0.35 g, 1 mmol) in THF (1 ml) was added. The mixture was stirred at -40° C. for 1 h before acetic acid (0.1 ml) was added. The mixture was allowed to warm to room temperature, diluted with 100 ml of hexane, washed with water, NaHCO3 saturated, and brine and then dried over MgSO4. Solvents were flash-evaporated (20 Torr, 30° C.) and the oily residue purified by chromatography on silica gel 25 g, 230-400 mesh, eluant: petroleum ether (100 ml), then petroleum ether/EtOAc: 95/5 (200 ml), then petroleum ether/EtOAc: 92/8. The product containing fractions were combined and solvents removed in vacuo to afford 0.13 g of pure (8R,11R,12R,15R,16R)-11,15-di-t.butyldimethylsilyloxy-16-methoxy-9-oxo-prost-13-en-1-oic acid, methyl ester.

Workup

  1. temperatureThe reaction mixture was warmed to -40° C.
  2. stirringstirred for 1 h when a solution of the (3R)3-t
  3. additionwas added
  4. temperatureto warm to room temperature
  5. washwashed with water, NaHCO3 saturated, and brine
  6. dry with materialdried over MgSO4
  7. customSolvents were flash-evaporated (20 Torr, 30° C.)
  8. customthe oily residue purified by chromatography on silica gel 25 g, 230-400 mesh, eluant
  9. additionThe product containing fractions
  10. customsolvents removed in vacuo
  11. customto afford 0.13 g of pure (8R,11R,12R,15R,16R)-11,15-di-t

Sources & evidence

ORD record
ord-f75bd848c6d34d48b0a2421d42a8f91f
Source dataset
uspto-grants-1991_10
Patent number
US05055592

Reaction notes

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