Diethyl (cyanomethyl)phosphonate → (3-{[Tert-butyl(diphenyl)silyl]oxy}cyclobutylidene)acetonitrile

HRID 1966168Notes

Reaction equation

HRID 1966168 reaction equation
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].[Si:18]([O:35][CH:36]1[CH2:39][C:38](=O)[CH2:37]1)([C:31]([CH3:34])([CH3:33])[CH3:32])([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>O1CCCC1>[Si:18]([O:35][CH:36]1[CH2:37][C:38](=[CH:9][C:7]#[N:8])[CH2:39]1)([C:31]([CH3:33])([CH3:34])[CH3:32])([C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

5

Reactant 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 23665647Potassium tert-butoxideHCID 668245053-((tert-Butyldiphenylsilyl)oxy)cyclobutanone

Product 1

HCID 66824450(3-{[Tert-butyl(diphenyl)silyl]oxy}cyclobutylidene)acetonitrileYield 74.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To 1.0 M of potassium tert-butoxide in tetrahydrofuran (1.2 mL) was added dropwise, at 0° C., diethyl cyanomethylphosphonate (0.19 mL, 0.0012 mol). The reaction was warmed to rt and 30 min later cooled to 0° C. again. To the reaction mixture was added a solution of 3-[tert-butyl(diphenyl)silyl]oxycyclobutanone (0.25 g, 0.00077 mol) in THF (5 mL). The reaction was allowed to warm up to rt gradually and stirred at rt for 2 h. The reaction was quenched with saturated aq. NH4Cl, extracted with EtOAc. The combined organic layers were washed with brine, dried over MgSO4, concentrated. The resultant residue was purified with Combiflash (silica gel, 0-20% EtOAc/Hex) to give the desired product (0.2 g) as colorless oil. LCMS calculated for C22H26NOSi(M+H)+: 348.1 Found: 348.3.

Workup

  1. temperaturelater cooled to 0° C. again
  2. temperatureto warm up to rt gradually
  3. customThe reaction was quenched with saturated aq. NH4Cl
  4. extractionextracted with EtOAc
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. customThe resultant residue was purified with Combiflash (silica gel, 0-20% EtOAc/Hex)

Sources & evidence

ORD record
ord-fbd77ee36538480bbd10a46ed8df84e0
Source dataset
uspto-grants-2013_04
Patent number
US08420629B2

Reaction notes

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