Hexane → tert-Butyl 6-cyano-5-(tert-butyldiphenylsilyloxy)-3-oxohexanoate

HRID 226274Notes

Reaction equation

HRID 226274 reaction equation
C([Li])CCC.CCCCCC.[C:12]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])(=[O:14])[CH3:13].[C:20]([CH2:22][CH:23]([O:30][Si:31]([C:44]([CH3:47])([CH3:46])[CH3:45])([C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[CH2:24][C:25](OCC)=[O:26])#[N:21]>C1COCC1.O.CO>[C:20]([CH2:22][CH:23]([O:30][Si:31]([C:44]([CH3:47])([CH3:46])[CH3:45])([C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)[C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1)[CH2:24][C:25](=[O:26])[CH2:13][C:12]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])#[N:21]

Participants

8

Reactant 4

HCID 8058HexaneHCID 10908tert-Butyl acetateHCID 11718177Ethyl 4-cyano-3-(tert-butyldiphenylsilyloxy)-butanoateHCID 178418339Butyllithium

Product 1

HCID 11532812tert-Butyl 6-cyano-5-(tert-butyldiphenylsilyloxy)-3-oxohexanoate

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-7.5 °C

Procedure

A solution of n-butyl lithium in hexane (14.4 ml, 0.21 mol) was added to a chilled solution (−5 to −10° C.) of diisopropylamlie (23.2 g, 0.23 mol) in THF (100 ml) and the resulting mixture was stirred at −5 to −10° C. for 30 minutes. After chilling the reaction to about −45° C., tert-butyl acetate (26 g, 0.21 mol) was added and the resulting reaction mixture was stirred at −20-30° C. for 1 hour. A solution of ethyl 4-cyano-3-(tert-butyldiphenylsilyloxy)-butanoate (20 g, 0.050 mol) in THF (20 ml) was added to the reaction mixture at about −75° C. and further stirred −70-−75° C. for 2 hours. Methanol (15 ml) was added to the reaction mixture followed by water (200 ml) and layers were separated. The organic layer was preserved. The aqueous layer was extracted with ethyl acetate (2×200 ml) and combined with the organic layer. The combined organic layer was evaporated to give the title compound.

Workup

  1. temperatureAfter chilling
  2. customthe reaction to about −45° C.
  3. customthe resulting reaction mixture
  4. stirringwas stirred at −20-30° C. for 1 hour
  5. customwere separated
  6. extractionThe aqueous layer was extracted with ethyl acetate (2×200 ml)
  7. customThe combined organic layer was evaporated

Sources & evidence

ORD record
ord-049528c9a0f14b43ba15627cb5353389
Source dataset
uspto-grants-2009_07
Patent number
US07557238B2

Reaction notes

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