Triphenylphosphine → HCID 15867806, compound

HRID 1604114Notes

Reaction equation

HRID 1604114 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.FC(F)(F)S(O[C:26]1[CH2:40][C@@H:39]([O:41][Si:42]([C:45]([CH3:48])([CH3:47])[CH3:46])([CH3:44])[CH3:43])[C@H:38](/[CH:49]=[CH:50]/[C@@H:51]([O:59][Si:60]([C:63]([CH3:66])([CH3:65])[CH3:64])([CH3:62])[CH3:61])[CH2:52][C@H:53]([CH3:58])[CH2:54][CH2:55][CH2:56][CH3:57])[C:27]=1[S:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][C:34]([O:36][CH3:37])=[O:35])(=O)=O.[O-][Si]([O-])=O.[Mg+2].[F:74][C:75](I)([F:77])[F:76]>O1CCCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].[Zn]>[F:74][C:75]([F:77])([F:76])[C:26]1[CH2:40][C@@H:39]([O:41][Si:42]([C:45]([CH3:48])([CH3:47])[CH3:46])([CH3:43])[CH3:44])[C@H:38](/[CH:49]=[CH:50]/[C@@H:51]([O:59][Si:60]([C:63]([CH3:66])([CH3:65])[CH3:64])([CH3:61])[CH3:62])[CH2:52][C@H:53]([CH3:58])[CH2:54][CH2:55][CH2:56][CH3:57])[C:27]=1[S:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][C:34]([O:36][CH3:37])=[O:35]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 16843Trifluoroiodomethane2×HCID 61680MAGNESIUM SILICATE (synthetic)HCID 15867790HCID 15867790, compound

Product 1

HCID 15867806HCID 15867806, compoundYield 36%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Tris(dibenzylideneacetone)dipalladium(0) (11.4 mg, 0.0125 mmol), triphenylphosphine (13.1 mg, 0.05 mmol), zinc (powder) (36.8 mg, 56.3 mmol), and methyl (11R,12S,13E,15S,17R)-9-trifluoromethanesulfonyloxy-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethyl-7-thiaprosta-8,13-dienoate (218 mg, 0.282 mmol) in tetrahydrofuran (5 mL) were placed in an autoclave reactor, a small sized container of trifluoromethyl iodide was connected, and the inside of the reaction vessel was made the same pressure as the inside of the small sized container. The reaction vessel was made to vibrate in trifluoromethyl iodide atmosphere for 1 hour by an ultrasonic wave washer. Next, the unreacted trifluoromethyl iodide in the reaction vessel was removed to obtain the reaction solution which was passed through Florisil column. The solution thus obtained was concentrated under reduced pressure, then was purified by silica gel column chromotography (4to 10% ethyl acetate/hexane) to obtain methyl (11R,12S,13E,15S,17R)-9-trifluoromethyl-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethyl-7-thiaprosta-8,13-dienoate (72 mg, 36%).

Workup

  1. customfor 1 hour
  2. customNext, the unreacted trifluoromethyl iodide in the reaction vessel was removed
  3. customto obtain the reaction solution which
  4. customThe solution thus obtained
  5. concentrationwas concentrated under reduced pressure
  6. customwas purified by silica gel column chromotography (4to 10% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-84487974cd6e4ec48337f5619ea94f81
Source dataset
uspto-grants-1999_11
Patent number
US05990346

Reaction notes

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