1,4-Dioxaspiro[4.5]decan-8-one → 8-Methylidene-1,4-dioxaspiro[4.5]decane

HRID 535322Notes

Reaction equation

HRID 535322 reaction equation
[Li][CH2:2][CH2:3][CH2:4][CH3:5].[O:6]1[C:10]2(CCC(=O)[CH2:12][CH2:11]2)[O:9][CH2:8][CH2:7]1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH2:5]=[C:4]1[CH2:12][CH2:11][C:10]2([O:9][CH2:8][CH2:7][O:6]2)[CH2:2][CH2:3]1

Participants

5

Reactant 2

HCID 5674151,4-Dioxaspiro[4.5]decan-8-oneHCID 178418339Butyllithium

Product 1

HCID 109537438-Methylidene-1,4-dioxaspiro[4.5]decane

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A solution of n-BuLi (2.5 M in hexanes, 30 ml, 75 mmol) was slowly added to a suspension of methyltriphenylphosphonium bromide (28.07 g, 79 mmol) in THF (150 ml) at −10° C. After stirring for 1 h, 1,4-dioxaspiro[4.5]decan-8-one (8.01 g, 51.3 mmol) was added. The reaction was warmed to room temperature and stirred for 4 h. The reaction was quenched with sat. aq. NH4Cl and extracted by diethyl ether. The combined organic extracts were dried (Na2SO4), concentrated at 200 mbar and 30° C. The residue was diluted with DCM and hexanes (1:1), and the solid was filtered. The organic extracts were concentrated at 200 mbar and 30° C., followed by silica gel chromatography (EtOAc/hexanes: 0-10%-20% gradient) to afford the title compound.

Workup

  1. stirringstirred for 4 h
  2. customThe reaction was quenched with sat. aq. NH4Cl
  3. extractionextracted by diethyl ether
  4. dry with materialThe combined organic extracts were dried (Na2SO4)
  5. concentrationconcentrated at 200 mbar and 30° C
  6. additionThe residue was diluted with DCM and hexanes (1:1)
  7. filtrationthe solid was filtered
  8. concentrationThe organic extracts were concentrated at 200 mbar and 30° C.

Sources & evidence

ORD record
ord-d9b925dd97c140db8d298dc68517d37c
Source dataset
uspto-grants-2014_10
Patent number
US08859535B2

Reaction notes

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