HCID 86609128, compound → HCID 86609127, compound

HRID 902340Notes

Reaction equation

HRID 902340 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([O:11][CH2:12][C@H:13]([O:16][C:17]2[C:22]([CH2:23]C=C)=[CH:21][CH:20]=[CH:19][C:18]=2[C:26]2[C:31]([Cl:32])=[CH:30][CH:29]=[CH:28][C:27]=2[Cl:33])[CH:14]=[CH2:15])(=[O:10])=[O:9])=[CH:4][CH:3]=1.[H][H]>ClCCl.C(OCC)(=O)C.C(O)C.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1.C1C=CC(C=[Ru](Cl)Cl)=CC=1.[Pt](=O)=O>[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([O:11][CH2:12][C@H:13]2[CH2:14][CH2:15][CH2:23][C:22]3[CH:21]=[CH:20][CH:19]=[C:18]([C:26]4[C:31]([Cl:32])=[CH:30][CH:29]=[CH:28][C:27]=4[Cl:33])[C:17]=3[O:16]2)(=[O:10])=[O:9])=[CH:4][CH:3]=1

Participants

8

Reactant 2

HCID 86609128HCID 86609128, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 86609127HCID 86609127, compoundYield 92.4%

Reagents, catalysts & solvents 5

HCID 345198Adams' catalystCatalystHCID 11967259Benzylidenebis(tricyclohexylphosphine)dichlororutheniumCatalystHCID 702EthanolSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of (2R)-2-[(3-allyl-2′,6′-dichlorobiphenyl-2-yl)oxy]but-3-en-1-yl 4-methylbenzenesulfonate (702 mg, 1.394 mmol) in anhydrous dichloromethane (35 mL) at room temperature under nitrogen was added benzylidene-bis(tricyclohexylphosphine)dichlororuthenium (114 mg, 0.1394 mmol) and the reaction mixture stirred at room temperature for 5 hours. The reaction mixture was then concentrated under reduced pressure to afford a brown syrup. The crude product was dissolved in ethyl acetate (7 mL) and the solution added to a suspension of platinum (IV) oxide (32 mg, 0.139 mmol) in absolute ethanol (21 mL). The mixture was then hydrogenated at 12 psi of hydrogen for 1 hour. The reaction mixture was filtered through celite and the filtrate concentrated under reduced pressure to afford a brown syrup. Purification by flash chromatography using a solvent gradient of 3 to 10% ethyl acetate in hexane afforded 0.615 g (92%) of [(2R)-9-(2,6-dichlorophenyl)-2,3,4,5-tetrahydro-1-benzoxepin-2-yl]methyl 4-methylbenzenesulfonate as a yellow solid. MS (ESI) m/z 477 ([M+H]+).

Workup

  1. concentrationThe reaction mixture was then concentrated under reduced pressure
  2. customto afford a brown syrup
  3. filtrationThe reaction mixture was filtered through celite
  4. concentrationthe filtrate concentrated under reduced pressure
  5. customto afford a brown syrup
  6. customPurification by flash chromatography

Sources & evidence

ORD record
ord-9f7c524074214edebb6661e974c60053
Source dataset
uspto-grants-2008_04
Patent number
US07365095B2

Reaction notes

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