7-Bromo-1-heptene → Tert-butyl 1-(hept-6-enyl)cyclopropylsulfonylcarbamate

HRID 2061419Notes

Reaction equation

HRID 2061419 reaction equation
[CH:1]1([S:4]([NH:7][C:8](=[O:14])[O:9][C:10]([CH3:13])([CH3:12])[CH3:11])(=[O:6])=[O:5])[CH2:3][CH2:2]1.C([Li])CCC.Br[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH:26]=[CH2:27]>C1COCC1>[CH2:27]([C:1]1([S:4]([NH:7][C:8](=[O:14])[O:9][C:10]([CH3:11])([CH3:13])[CH3:12])(=[O:6])=[O:5])[CH2:2][CH2:3]1)[CH2:26][CH2:25][CH2:24][CH2:23][CH:22]=[CH2:21]

Participants

5

Reactant 3

HCID 5244507-Bromo-1-hepteneHCID 20773763tert-Butyl (cyclopropanesulfonyl)carbamateHCID 178418339Butyllithium

Product 1

HCID 59366234Tert-butyl 1-(hept-6-enyl)cyclopropylsulfonylcarbamateYield 44.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl cyclopropylsulfonylcarbamate (885 mg, 4 mmol) in THF (20 mL) at −78° C. was added n-Butyllithium (3.36 mL, 8.40 mmol) (2.5 M in hexanes) dropwise. The formed solution was warmed up to r.t. and stirred for 1.5 h. Cooled this light yellow solution back to −78° C. 7-Bromo-1-heptene (1.219 mL, 8.00 mmol) was added dropwise. The final solution was allowed to warm up to r.t. over the period of 16 h. Quenched with sat. NH4Cl, extracted with EtOAc. The organic layer was washed with brine, dried over MgSO4, filtered, and concentrated. The residue was purified by Biotage column, eluted with gradient 5%˜40% EtOAc-Hexane to afford the desired product tert-butyl 1-(hept-6-enyl)cyclopropylsulfonylcarbamate (625 mg, 1.772 mmol, 44.3% yield) as a viscous oil, which solidified upon standing on bench. 1H NMR (400 MHz, CHLOROFORM-D) ppm 0.88-1.02 (m, 2 H) 1.26-1.49 (m, 6 H) 1.53 (s, 9 H) 1.60-1.71 (m, 2 H) 1.82-1.94 (m, 2 H) 2.06 (q, J=6.94 Hz, 2 H) 4.81-5.08 (m, 2 H) 5.68-5.88 (m, 1 H) 6.88 (b, NH). LC-MS (retention time: 2.76 min, Method A), MS m/z 218 (M+H-Boc).

Workup

  1. temperatureCooled this light yellow solution back to −78° C
  2. temperatureto warm up to r.t. over the period of 16 h
  3. customQuenched with sat. NH4Cl
  4. extractionextracted with EtOAc
  5. washThe organic layer was washed with brine
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by Biotage column
  10. washeluted with gradient 5%˜40% EtOAc-Hexane

Sources & evidence

ORD record
ord-ab3d540ffcd941f78f99e87d07351b8b
Source dataset
uspto-grants-2012_10
Patent number
US08283310B2

Reaction notes

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