Iodine → HCID 131720982, compound

HRID 1604073Notes

Reaction equation

HRID 1604073 reaction equation
[CH:1]1([CH2:7][CH2:8][CH2:9][CH2:10][NH:11][C:12]([C:14]2[N:15]=[C:16]([C:19]3[CH:24]=[CH:23][C:22](/[C:25](/[Sn](CCCC)(CCCC)CCCC)=[CH:26]\[CH2:27][CH2:28][CH2:29][C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])=[CH:21][CH:20]=3)[O:17][CH:18]=2)=[O:13])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[I:50]I>C1COCC1>[CH:1]1([CH2:7][CH2:8][CH2:9][CH2:10][NH:11][C:12]([C:14]2[N:15]=[C:16]([C:19]3[CH:24]=[CH:23][C:22](/[C:25](/[I:50])=[CH:26]\[CH2:27][CH2:28][CH2:29][C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])=[CH:21][CH:20]=3)[O:17][CH:18]=2)=[O:13])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1

Participants

4

Reactant 2

HCID 807IodineHCID 15462463HCID 15462463, compound

Product 1

HCID 131720982HCID 131720982, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A 2-necked 50 mL round bottom flask was charged under nitrogen atmosphere with a stir bar, the above alkyne (148.6 mg, 0.302 mmol), and tetrakis(triphenylphosphine)palladium(0) (17.4 mg, 0.0015 mmol). Anhydrous toluene (5 mL) was added via syringe, and the mixture was stirred until the two solids dissolved. A 2 mL solution of tributyltin hydride (0.392 mmol) in anhydrous toluene was added, and the reaction stirred at room temperature for 30 minutes. The solution was then transferred to a dry 50 mL round bottom flask and the toluene was removed in vacuo to afford tert-butyl (E)-6-[4-[4-[[(4-cyclohexylbutyl)amino]carbonyl]-2-oxazolyl]phenyl]-6-(tributylstannyl)hex-5-enoate as a residue which was used directly. The stannane was dissolved in 10 mL anhydrous THF and the flask was cooled to 0° C. in an ice bath. A 10 mL solution of iodine (84.2 mg, 0.3318 mmol) in anhydrous THF was added dropwise via pressure equalizing addition funnel over 30 minutes. The ice bath was removed and the reaction stirred at room temperature for 2 hours. Saturated sodium bisulfite solution (50 mL) was added, and the organics were extracted three times with ethyl acetate. The combined extracts were dried over MgSO4. Filtration and solvent removal gave a yellow oil which was purified by radial chromatography (2 mm plate, 10% ethyl acetate in hexanes) to give 193.6 mg of a pale yellow oil: 1H NMR (CDCl3) δ8.24 (s, 1H), 8.00 (d, 2H), 7.41 (d, 2H), 7.05 (broad t, 1H), 6.52 (t, 1H), 3.45 (q, 2H), 2.15 (q, 2H), 2.04 (q, 2H), 1.70 (m, 7H), 1.40 (m, 9H), 1.23 (m, 6H), 0.93 (m, 4H); IR (cm-1) 2926, 2853, 1721, 1664, 1599. High Resolution MS Accurate mass calculated for C30H42IN2O4 : 621.2189. Found: 621. 2183.

Workup

  1. additionaddition funnel over 30 minutes
  2. customThe ice bath was removed
  3. additionSaturated sodium bisulfite solution (50 mL) was added
  4. extractionthe organics were extracted three times with ethyl acetate
  5. dry with materialThe combined extracts were dried over MgSO4
  6. filtrationFiltration and solvent removal
  7. customgave a yellow oil which
  8. customwas purified by radial chromatography (2 mm plate, 10% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-00ba97a605f0483ab52f4c626c1001cb
Source dataset
uspto-grants-1999_11
Patent number
US05990308

Reaction notes

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