Hexane → HCID 15867797, compound

HRID 1604108Notes

Reaction equation

HRID 1604108 reaction equation
[C:1]1(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.C[Al](C)C.CCCCCC>ClCCCl.Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.CCOCC>[CH3:1][C:26]1[CH2:40][C@@H:39]([O:41][Si:42]([C:45]([CH3:47])([CH3:46])[CH3:48])([CH3:43])[CH3:44])[C@H:38](/[CH:49]=[CH:50]/[C@@H:51]([O:59][Si:60]([C:63]([CH3:66])([CH3:64])[CH3:65])([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

10

Reactant 4

HCID 8058HexaneHCID 11776TriphenylphosphineHCID 15867790HCID 15867790, compoundHCID 16682925Trimethylaluminum

Product 1

HCID 15867797HCID 15867797, compoundYield 55.1%

Reagents, catalysts & solvents 5

HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 111,2-DichloroethaneSolventHCID 313Hydrochloric AcidSolventHCID 3283Diethyl EtherSolvent

Procedure

To tetrakistriphenylphosphinepalladium prepared in advance in the system from tris(dibenzylideneacetone) dipalladium(0) (92 mg, 0.1 mmol) and triphenylphosphine (210 mg, 0.8 mmol) were added methyl (11R,12S,13E,15S,17R)-9-trifluoromethanesulfonyloxy-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethyl-7-thiaprosta-8,13-dienoate 437 mg, 0.546 mmol) in 1,2-dichloroethane (5 mL) and 2M trimethylaluminum in hexane (0.423 mL, 0.846 mmol). This was agitated for 3 hours at room temperature. Ether was added to dilute the reaction solution, then the solution was poured in 1N hydrochloric acid. The desired product was extracted with ether from the mixture. The extract was washed with brine, then was dried over anhydrous sodium sulfate. The solution was concentrated under reduced pressure, then was purified by silica gel column chromotography (2% ethyl acetate/hexane) to obtain methyl (11R,12S,13E,15S,17R)-9-methyl-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethyl-7-thiaprosta-8,13-dienoate (193 mg, 54%).

Workup

  1. additionto dilute the reaction solution
  2. extractionThe desired product was extracted with ether from the mixture
  3. washThe extract was washed with brine
  4. dry with materialwas dried over anhydrous sodium sulfate
  5. concentrationThe solution was concentrated under reduced pressure
  6. customwas purified by silica gel column chromotography (2% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-d87e7d7b2e5b4dd8a3fb070ba85f22f5
Source dataset
uspto-grants-1999_11
Patent number
US05990346

Reaction notes

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