Iodine → HCID 86680653, compound

HRID 1615412Notes

Reaction equation

HRID 1615412 reaction equation
[C:1]1([C@@H:7]2[CH2:12][O:11][CH2:10][CH2:9][N:8]2[C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.FC(F)(F)C(O[I:25](C1C=CC=CC=1)OC(=O)C(F)(F)F)=O.II.IC1C=CC=CC=1>C(Cl)Cl.CCCCC>[I:25][C:4]1[CH:3]=[CH:2][C:1]([C@@H:7]2[CH2:12][O:11][CH2:10][CH2:9][N:8]2[C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])=[CH:6][CH:5]=1

Participants

7

Reactant 4

HCID 807IodineHCID 11575IodobenzeneHCID 102317Bis(trifluoroacetoxy)iodobenzeneHCID 86680652HCID 86680652, compound

Product 1

HCID 86680653HCID 86680653, compoundYield 37%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8003PentaneSolvent

Procedure

To a solution of (R)-tert-butyl 3-phenylmorpholine-4-carboxylate 7 (41.55 g, 157.66 mmol) in CH2Cl2 (400 mL) was added [bis(trifluoroacetoxy)-iodo]benzene (74.25 g, 172.7 mmol, 1.1 eq.) followed by I2 (40 g, 157.6 mmol, 1 eq.) at room temperature (The reaction was exothermic on this scale, the temperature was maintained at room temperature by means of a water bath!). The reaction mixture was stirred at room temperature for 30 minutes. The reaction mixture was diluted with CH2Cl2 (˜200 mL) and washed with sat. aq. NaHCO3 (2×750 mL), sat. aq. Na2S2O3 (2×500 mL) and brine (1 L). The organic layer was dried over Na2SO4 filtered and concentrated in vacuo leading to a brown oil containing the desired product. The residue was purified by automated column chromatography (silica column (1.6 kg); gradient heptanes/EtOAc 0 to 15%). The separation was not optimal, the product-containing fractions were concentrated affording a white solid contaminated with some (˜10%) iodobenzene and starting material. Trituration in pentane (2 mL/g) afforded material of sufficient purity (22.7 g, 58.3 mmol) was isolated in 37% yield.

Workup

  1. washwashed with sat. aq. NaHCO3 (2×750 mL), sat. aq. Na2S2O3 (2×500 mL) and brine (1 L)
  2. dry with materialThe organic layer was dried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. additioncontaining the desired product
  6. customThe residue was purified by automated column chromatography (silica column (1.6 kg); gradient heptanes/EtOAc 0 to 15%)
  7. customThe separation
  8. concentrationthe product-containing fractions were concentrated
  9. customaffording a white solid
  10. customwas isolated in 37% yield

Sources & evidence

ORD record
ord-6a3796e3a78842918b5217b4acaccd4a
Source dataset
uspto-grants-2014_07
Patent number
US08765751B2

Reaction notes

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