Hydrochloric Acid → 2-Propanyl 4-[(3S,5aR,6R,7R,8aS)-7-(tetrahydro-2H-pyran-2-yloxy)-6-vinyloctahydro-2H-cyclopenta[b]oxepin-3-yl]butanoate

HRID 573534Notes

Reaction equation

HRID 573534 reaction equation
[CH3:1][Si](C)(C)N[Si](C)(C)C.[Na].[CH:11]([C@@H:13]1[C@@H:22]2[C@@H:16]([O:17][CH2:18][C@@H:19]([CH2:23][CH2:24][CH2:25][C:26]([O:28][CH:29]([CH3:31])[CH3:30])=[O:27])[CH2:20][CH2:21]2)[CH2:15][C@H:14]1[O:32][CH:33]1[CH2:38][CH2:37][CH2:36][CH2:35][O:34]1)=O.Cl>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[O:34]1[CH2:35][CH2:36][CH2:37][CH2:38][CH:33]1[O:32][C@@H:14]1[CH2:15][C@@H:16]2[O:17][CH2:18][C@@H:19]([CH2:23][CH2:24][CH2:25][C:26]([O:28][CH:29]([CH3:31])[CH3:30])=[O:27])[CH2:20][CH2:21][C@@H:22]2[C@H:13]1[CH:11]=[CH2:1]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 45051731Sodium hexamethyidisilazaneHCID 866653202-Propanyl 4-[(3S,5aR,6R,7R,8aS)-6-formyl-7-(tetrahydro-2H-pyran-2-yloxy)octahydro-2H-cyclopenta[b]oxepin-3-yl]butanoate

Product 1

HCID 867043622-Propanyl 4-[(3S,5aR,6R,7R,8aS)-7-(tetrahydro-2H-pyran-2-yloxy)-6-vinyloctahydro-2H-cyclopenta[b]oxepin-3-yl]butanoate

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Methyltriphenylphosphonium bromide (2.60 g) was suspended in THF (10 mL), and followed by cooling to 0° C. Sodium hexamethyldisilazane (7.0 mL, 1 mol/L THF solution) was added, followed by stirring at the same temperature for 30 minutes. A THF (1 mL) solution of the compound (1.0 g) produced in Example 13 was added dropwise, followed by stirring at the same temperature for 1 hour. An extract obtained by pouring the reaction solution to 1 N hydrochloric acid cooled to 0° C. and extracting with ethyl acetate was washed with water, an aqueous saturated sodium bicarbonate solution and a saturated saline; dried with anhydrous magnesium sulfate; and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain a titled compound (967 mg) having the following physical property values.

Workup

  1. stirringby stirring at the same temperature for 1 hour
  2. customAn extract obtained
  3. temperaturecooled to 0° C.
  4. extractionextracting with ethyl acetate
  5. washwas washed with water
  6. dry with materialdried with anhydrous magnesium sulfate
  7. concentrationand then concentrated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-bd540076a60543fd9d194c3f5b1d297e
Source dataset
uspto-grants-2015_05
Patent number
US09029574B2

Reaction notes

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