Pyrrolizinium, 1,2,3,5,6,7-hexahydro-, perchlorate → 7a-ethynylhexahydro-1H-pyrrolizine

HRID 611575Notes

Reaction equation

HRID 611575 reaction equation
Cl([O-])(=O)(=O)=O.[CH2:6]1[C:13]2[CH2:12][CH2:11][CH2:10][N+:9]=2[CH2:8][CH2:7]1.[C:14]([Mg]Br)#[CH:15]>C1COCC1>[C:14]([C:13]12[CH2:12][CH2:11][CH2:10][N:9]1[CH2:8][CH2:7][CH2:6]2)#[CH:15]

Participants

4

Reactant 2

HCID 10878400Pyrrolizinium, 1,2,3,5,6,7-hexahydro-, perchlorateHCID 178418486HCID 178418486, compound

Product 1

HCID 195976957a-ethynylhexahydro-1H-pyrrolizineYield 71%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

The compound from step 15a above (1.0 g, 4.8 mmol) was added to a solution of 0.5 M ethynylmagnesium bromide (29 mL, 14.3 mmol) in THF at room temperature. The reaction mixture was stirred for 45 minutes, quenched with 15% NaOH solution, and diluted with brine:water (1:1). The aqueous phase was extracted with CH2Cl2, and the organic phases were combined, dried (MgSO4), concentrated and chromatographed (silica gel; CHCl3 /MeOH, 90:10) to afford an amber oil (463 mg, 71%): 1H NMR (CDCl3, 300 MHz) δ 1.75-2.06 (m, 6H), 2.14-2.23 (m, 2H), 2.33 (s, 1H), 2.53-2.62 (m, 2H), 322-3.28 (m, 2H); MS (CI/NH3) m/z: 136 (M+H)+.

Workup

  1. customquenched with 15% NaOH solution
  2. additiondiluted with brine:water (1:1)
  3. extractionThe aqueous phase was extracted with CH2Cl2
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customchromatographed (silica gel; CHCl3 /MeOH, 90:10)

Sources & evidence

ORD record
ord-7c193c6b89e0489a88a8cce43796b9e1
Source dataset
uspto-grants-1999_12
Patent number
US06001849

Reaction notes

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