Chlorotrimethylsilane → HCID 18403062, compound

HRID 1937327Notes

Reaction equation

HRID 1937327 reaction equation
[CH2:1]([PH:8](=[O:10])[OH:9])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.C[Si](Cl)(C)C.[CH2:23]([O:30][C:31]([CH:33]([CH2:46][CH2:47][C:48]([O:50][CH2:51][C:52]1[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1)=[O:49])[CH2:34]P(C)(=O)OCC1C=CC=CC=1)=[O:32])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1>ClCCl>[CH2:1]([P:8]([CH2:34][CH:33]([C:31]([O:30][CH2:23][C:24]1[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1)=[O:32])[CH2:46][CH2:47][C:48]([O:50][CH2:51][C:52]1[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=1)=[O:49])(=[O:9])[OH:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 15885218HCID 15885218, compoundHCID 178527042HCID 178527042, compound

Product 1

HCID 18403062HCID 18403062, compoundYield 30.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

Benzylphosphinic acid (2.3 g, 15 mmol) in 150 mL of dry dichloromethane was cooled to 0° C. under a nitrogen atmosphere. Triethylamine (6.5 g, 65 mmol) was added followed by trimethylsilyl chloride (5.8 g, 54 mmol) while the reaction temperature was maintained at 0° C. After 30 minutes dibenzyl 2-methylene-pentanedioate (2) (4.4 g, 13.6 mmol) in 20 mL of dichloromethane was added over 5 minutes. The reaction mixture was allowed to warm to room temperature and stirred overnight. The clear solution was cooled to 0° C. and quenched with 5% hydrochloric acid followed by removal of the organic layer. The organic layer was washed with 5% hydrochloric acid and with brine, dried (MgSO4) and evaporated to give a clear yellow liquid. Purification by flash chromatography and elution with 1:1 hexane/ethyl acetate containing 10% acetic acid yielded 2.0 g (28%) of benzyl[2,4-di(benzyloxycarbonyl)butyl]-phosphinic acid (3, R=CH2Ph, R1=H) as a clear light yellow oil. Rf 0.37 (1:1 Hexane/EtOAc, 10% AcOH).

Workup

  1. temperatureto warm to room temperature
  2. temperatureThe clear solution was cooled to 0° C.
  3. customquenched with 5% hydrochloric acid
  4. customfollowed by removal of the organic layer
  5. washThe organic layer was washed with 5% hydrochloric acid and with brine
  6. dry with materialdried (MgSO4)
  7. customevaporated
  8. customto give a clear yellow liquid
  9. customPurification
  10. washby flash chromatography and elution with 1:1 hexane/ethyl acetate containing 10% acetic acid

Sources & evidence

ORD record
ord-b51477d45f29480baab88750b2ea94c3
Source dataset
uspto-grants-2002_05
Patent number
US06395718B1

Reaction notes

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