Imidazole → Tert-butyl 3-iodoazetidine-1-carboxylate

HRID 592866Notes

Reaction equation

HRID 592866 reaction equation
O[CH:2]1[CH2:5][N:4]([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])[CH2:3]1.N1C=CN=C1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[I:37]I.C([O-])(O)=O.[Na+]>C1(C)C=CC=CC=1>[I:37][CH:2]1[CH2:5][N:4]([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])[CH2:3]1

Participants

7

Reactant 5

HCID 795ImidazoleHCID 807IodineHCID 11776TriphenylphosphineHCID 516892Sodium BicarbonateHCID 2756801Tert-butyl 3-hydroxyazetidine-1-carboxylate

Product 1

HCID 11000522Tert-butyl 3-iodoazetidine-1-carboxylateYield 93.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A solution of tert-butyl 3-hydroxyazetidine-1-carboxylate (3.5 g, 0.020 mol) in toluene (200 mL) was treated with imidazole (4.08 g, 0.060 mol), triphenylphosphine (0.60 g, 0.040 mol), and iodine (7.62 g, 0.030 mol). The mixture was heated at 100° C. for 1 h. It was then cooled to room temperature and poured into saturated NaHCO3 solution (30 mL). Excess triphenylphosphine was destroyed by addition of iodine until iodine coloration persisted in organic layer. The mixture was washed with 5% Na2SO3 solution, dried over Na2SO4, and evaporated in vacuo. The residue was purified by silica-gel column chromatography to afford 206a (5.31 g, 93%). MS-ESI: [M+H]+ 284.

Workup

  1. temperatureIt was then cooled to room temperature
  2. customExcess triphenylphosphine was destroyed by addition of iodine until iodine coloration
  3. washThe mixture was washed with 5% Na2SO3 solution
  4. dry with materialdried over Na2SO4
  5. customevaporated in vacuo
  6. customThe residue was purified by silica-gel column chromatography

Sources & evidence

ORD record
ord-f8d6b780a2b443e7898ba34e7df34614
Source dataset
uspto-grants-2016_01
Patent number
US09238655B2

Reaction notes

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