Tetrahydrofuran → HCID 86754892, compound

HRID 1604847Notes

Reaction equation

HRID 1604847 reaction equation
[C:1]1([PH:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C1C[O:17]CC1.[Li]CCCC.Cl[CH2:25]/[CH:26]=[C:27]1\[C:28](=[CH2:69])[C@@H:29]([O:51][Si:52]([C:65]([CH3:68])([CH3:67])[CH3:66])([C:59]2[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=2)[C:53]2[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=2)[CH2:30][C@@H:31]([O:33][Si:34]([C:47]([CH3:50])([CH3:49])[CH3:48])([C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[CH2:32]\1>O>[C:65]([Si:52]([C:53]1[CH:54]=[CH:55][CH:56]=[CH:57][CH:58]=1)([C:59]1[CH:60]=[CH:61][CH:62]=[CH:63][CH:64]=1)[O:51][C@H:29]1[CH2:30][C@@H:31]([O:33][Si:34]([C:47]([CH3:48])([CH3:49])[CH3:50])([C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[C:35]2[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=2)[CH2:32]/[C:27](=[CH:26]/[CH2:25][P:7](=[O:17])([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)/[C:28]1=[CH2:69])([CH3:66])([CH3:67])[CH3:68]

Participants

6

Reactant 4

HCID 8028Tetrahydrofuran2×HCID 70017DiphenylphosphineHCID 86754183(Z)-(3S,5S)-1-(2-chloroethylidene)-3,5-bis-(tert-butyl-diphenyl-silanyloxy)-2-methylenecyclohexaneHCID 178418339Butyllithium

Product 1

HCID 86754892HCID 86754892, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

847 μl (10.2 mmol) of diphenylphosphine in 16 ml of abs. THF was deprotonated at -10° with 3.05 ml nBuLi (1.5 M, hexane). The solution was then cooled to -75° and 2.76 g (4.15 mmol) of (Z)-(3S,5S)-1-(2-chloroethylidene)-3,5-bis-(tert-butyl-diphenyl-silanyloxy)-2-methylenecyclohexane, dissolved in 16 ml of abs. THF, was added dropwise. 10 Minutes later, 190 μl of water was injected and the reaction mixture allowed to reach room temperature. All solvents were then removed i.V., the residue taken up in 33 ml of CH2Cl2 and treated with 81 ml of 5% H2O2. After stirring for 75 minutes, the layers were separated, the aqueous phase extracted with AcOEt, the organic layers washed with sodium pyrosulfite, dried over sodium sulfate and evaporated to dryness. Flash chromatography (SiO2, hexane/AcOEt=45/55) afforded 2.534 g of (Z)-(3S,5S)-[2[-3,5-bis-(tert-butyl-diphenyl-silanyloxy)-2-methylenecyclohexylidene]-ethyl]-diphenyl-phosphine oxide as colorless foam.

Workup

  1. temperatureThe solution was then cooled to -75°
  2. customto reach room temperature
  3. customAll solvents were then removed i.V
  4. additiontreated with 81 ml of 5% H2O2
  5. customthe layers were separated
  6. extractionthe aqueous phase extracted with AcOEt
  7. washthe organic layers washed with sodium pyrosulfite
  8. dry with materialdried over sodium sulfate
  9. customevaporated to dryness

Sources & evidence

ORD record
ord-8d9f1deaa6124001b53f4435bb377e6e
Source dataset
uspto-grants-1999_11
Patent number
US05994569

Reaction notes

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