HCID 14136727, compound → HCID 86691656, compound

HRID 2406868Notes

Reaction equation

HRID 2406868 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].[C:6]12(C(=O)C3C[CH:10]1[CH2:11][CH2:12]3)[CH2:9][CH2:8][CH2:7]2>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[CH2:4]=[C:3]1[C:6]2([CH2:9][CH2:8][CH2:7]2)[CH:10]2[CH2:1][CH:2]1[CH2:12][CH2:11]2

Participants

5

Reactant 2

HCID 14136727HCID 14136727, compoundHCID 178418339Butyllithium

Product 1

HCID 86691656HCID 86691656, compoundYield 75%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a suspension of (methyl)triphenylphosphonium bromide (49.9 mmol, 18.2 g) in dry tetrahydrofuran (THF) (100 mL) at −78° C. was added n-butyllithium (46.5 mmol, 18.6 mL of 2.5 M solution in hexanes). The mixture was stirred for 30 min at −78° C. To this mixture was added spiro[bicyclo[2.2.1]heptane-2,1′-cyclobutan]-3-one (5.00 g, 33.3 mmol). The resulting mixture was stirred at ambient temperature for 20 h. Hexanes (300 mL) were added, and the mixture was filtered. The filtrate was concentrated, and the residue was purified on an 80 g silica gel column, eluting with hexanes, to obtain 3-methylenespiro[bicyclo[2.2.1]heptane-2,1′-cyclobutane] (Compound III in Scheme 1) (3.7 g, 75%) as oil. 1H NMR (CDCl3, 400 MHz); δ 4.82 (s, 2H), 2.63 (bra, 1H), 2.22 (bra, 1H), 2.05-1.78 (m, 6H), 1.63-1.52 (m. 1H), 1.48-1.34 (m, 3H), 1.21-1.12 (m, 2H).

Workup

  1. stirringThe resulting mixture was stirred at ambient temperature for 20 h
  2. filtrationthe mixture was filtered
  3. concentrationThe filtrate was concentrated
  4. customthe residue was purified on an 80 g silica gel column
  5. washeluting with hexanes

Sources & evidence

ORD record
ord-46245ae7115e4344b0de1c8d16b03d8a
Source dataset
uspto-grants-2014_08
Patent number
US08809397B2

Reaction notes

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