Iodoform → HCID 86600623, compound

HRID 2245818Notes

Reaction equation

HRID 2245818 reaction equation
[Si:1]([O:8][C@H:9]([C@H:17]([O:20][Si:21]([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22])[CH:18]=O)[CH2:10][CH2:11][CH2:12][C:13]([O:15][CH3:16])=[O:14])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH:28]([I:31])(I)I>C1COCC1.[Cl-].[Cr+3].[Cl-].[Cl-]>[Si:1]([O:8][C@H:9]([C@H:17]([O:20][Si:21]([C:24]([CH3:25])([CH3:27])[CH3:26])([CH3:22])[CH3:23])/[CH:18]=[CH:28]/[I:31])[CH2:10][CH2:11][CH2:12][C:13]([O:15][CH3:16])=[O:14])([C:4]([CH3:5])([CH3:7])[CH3:6])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 6374Iodoform2×HCID 14463532HCID 14463532, compound

Product 1

HCID 86600623HCID 86600623, compoundYield 40%

Reagents, catalysts & solvents 2

HCID 6452300Chromium(3+) trichlorideCatalyst2×HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of (5S,6S)-methyl 5,6-bis(tert-butyldimethylsilyloxy)-7-oxoheptanoate (389 mg, 0.929 mmol) and iodoform (2.19 g, 5.57 mmol) in THF (20 mL) was allowed it to stir for about 10 min. In a separate round bottom flask added chromium chloride (II) (1.36 mg, 11.1 mmol) and dissolved it in THF (10 mL) and cooled the reaction mixture to 0° C. The aldehyde and iodoform mixture were transferred to a stirring solution of chromium chloride at 0° C., warmed to room temperature and allowed to stir for 3 h. The reaction was quenched with water, extracted with ether, dried, and concentrated. Purification by flash chromatography (silica gel, hexanes) afforded 200 mg (40% yield) of (5S,6R,E)-methyl 5,6-bis(tert-butyldimethylsilyloxy)-8-iodooct-7-enoate. 1H NMR (250 MHz, CDCl3): δ 6.46 (dd, J=14.9 Hz, J=7.2 Hz 1H), 6.18 (d, J=15.4 Hz, 1H), 3.85 (m, 1H), 3.63 (s, 3H), 3.52 (m, 1H), 2.27 (t, J=7.1 Hz, 3H), 1.62 (m, 2H), 1.47 (m, 2H), 0.850 (s, 9H), 0.849 (s, 9H), 0.023 (s, 6H), 0.013 (s, 3H), −0.005 (s, 3H).

Workup

  1. temperaturewarmed to room temperature
  2. stirringto stir for 3 h
  3. customThe reaction was quenched with water
  4. extractionextracted with ether
  5. customdried
  6. concentrationconcentrated
  7. customPurification by flash chromatography (silica gel, hexanes)

Sources & evidence

ORD record
ord-850b4d77ff504185ac8f4154e502d833
Source dataset
uspto-grants-2010_03
Patent number
US07683193B2

Reaction notes

Loading…